Articles including glass and/or glass-ceramics and methods of making the same

ABSTRACT

A glass-ceramic includes a silicate-containing glass and crystals within the silicate-containing glass. The crystals include non-stoichiometric tungsten and/or molybdenum sub-oxides, and the crystals are intercalated with dopant cations.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No. 16/404,783 filed on May 7, 2019, which is a continuation of U.S. application Ser. No. 16/157,663 filed on Oct. 11, 2018, which issued on Aug. 6, 2019 as U.S. Pat. No. 10,370,291 which is a continuation of U.S. application Ser. No. 15/840,040 filed on Dec. 13, 2017, which issued on Apr. 2, 2019 as U.S. Pat. No. 10,246,371, the contents of each of which is incorporated by reference herein in its entirety.

FIELD OF THE DISCLOSURE

The present disclosure generally relates to articles including glasses and/or glass-ceramics, and more specifically, to compositions and methods of forming such articles.

BACKGROUND

Ultraviolet (“UV”) and near-infrared (“NIR”) absorbing alkali containing silicate glass-ceramics are a class of glass-ceramics which exhibit optical properties dependent on the wavelength of light which is incident on the glass-ceramics. Conventional UV/IR-blocking glasses (with low or high visible transmittance) are formed by introducing certain cationic species (e.g., Fe²⁺ to absorb NIR wavelengths and Fe₂ ³⁺ to absorb UV wavelengths, and other dopants such as Co, Ni, and Se to modify the visible transmittance) which are bonded with the glass network. Traditionally, these glass-ceramics were produced by melting the constituents together to form a glass, followed by the in situ formation of submicron precipitates through a post-formation heat treatment to form the glass-ceramic. These submicroscopic precipitates (e.g., tungstate- and molybdate-containing crystals) are absorptive of wavelength bands of light giving the glass-ceramic its optical properties. Such conventional glass-ceramics could be produced in both transparent as well as opalized forms.

Conventional tungsten and molybdenum alkali containing silicate glasses were believed to be bound to a specific and narrow composition range in order to produce glasses and glass-ceramics that are transparent at visible wavelengths. The believed composition range was based on a perceived solubility limit of tungsten oxide within peralkaline glass. For example, when batched and melted in a conventional manner, tungsten oxide can react with alkali metal oxides in the batch to form a dense alkali tungstate liquid at a low temperature during the initial stages of the melt immediately after being put into a melting furnace (e.g., the reaction occurs at about 500° C.). Because of the high density of this phase, it rapidly segregates at the bottom of the crucible. At significantly higher temperatures (e.g., above about 1000° C.), silicate constituents start to melt, and because of the silicate constituents' lower density, it remains atop the alkali tungstate liquid. The difference in densities of the constituents results in a stratification of the different liquids which gives the appearance to those skilled in the art of an immiscibility with one another This effect was observed particularly when R₂O (e.g., Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O) minus Al₂O₃ was about 0 mol % or greater. The resulting apparent liquid immiscibility at melting temperature resulted in a tungsten-rich phase segregating and crystallizing as it cooled which manifested itself as an opalized, non-transparent, crystal. This issue was also present with molybdenum containing melts.

Those having ordinary skill in the art observed the tungsten- and/or molybdenum-rich phase separate from the silicate rich phase, they perceived a solubility limit of tungsten and/or molybdenum (e.g., about 2.5 mol %) within the silicate rich phase. The perceived solubility limit prevented the glass from ever becoming super-saturated with tungsten or molybdenum oxides, thereby preventing either constituent from being controllably precipitated through post-forming heat-treatment to produce a glass-ceramic with a crystalline phase including these elements. Thus, the perceived solubility prevented the development of glass-ceramic compositions which achieved a sufficient quantity of solubilized tungsten and/or molybdenum to allow the formation of tungsten and/or molybdenum containing wavelength dependent submicroscopic crystals through subsequent heat treatment.

In view of these limitations, there is a need for new compositions and methods of making them that facilitate improved near infrared and ultraviolet blocking (e.g., through higher tungsten and molybdenum solubility).

SUMMARY OF THE DISCLOSURE

It has been discovered that a homogenous single-phase W or Mo-containing peralkaline melt may be obtained through the use of “bound” alkalis as described herein. Exemplary bound alkalis may include feldspar, nepheline, borax, spodumene, other sodium or potassium feldspars, alkali-aluminum-silicates and/or other naturally occurring and artificially created minerals containing an alkali and one or more aluminum and/or silicon atoms. By introducing the alkali in the bound form, the alkalis may not react with the W or Mo present in the melt to form the dense alkali tungstate and/or alkali molybdate liquid. Moreover, this change in batch material may allow the melting of strongly peralkaline compositions (e.g., R₂O—Al₂O₃=about 2.0 mol % or more) without the formation of any alkali tungstate and/or alkali molybdate second phase. This has also allowed melt temperature and mixing method to be varied and still produce a single-phase homogenous glass.

According to at least one feature of the present disclosure, an article includes (a) a glass. The glass includes SiO₂ from about 25 mol % to about 99 mol %, Al₂O₃ from about 0 mol % to about 50 mol %, WO₃ plus MoO₃ from about 0.35 mol % to about 30 mol %, and R₂O from about 0.1 mol % to about 50 mol %. R₂O is one or more of Li₂O, Na₂O, K₂O, Rb₂O and Cs₂O. R₂O minus Al₂O₃ is from about −35 mol % to about 7 mol %. The glass includes at least one of: (i) RO from about 0.02 mol % to about 50 mol % and (ii) SnO₂ is from about 0.01 mol % to about 5 mol %. RO is one or more of MgO, CaO, SrO, BaO and ZnO. If WO₃ is from about 1 mol % to about 30 mol %, the glass further includes Fe₂O₃ of about 0.9 mol % or less or SiO₂ is from about 60 mol % to about 99 mol %. If WO₃ is from about 0.35 mol % to about 1 mol %, the glass includes SnO₂ from about 0.01 mol % to about 5.0 mol %. If MoO₃ is from about 1 mol % to about 30 mol %, SiO₂ is from about 61 mol % to about 99 mol % or Fe₂O₃ is about 0.4 mol % or less and R₂O is greater than RO. If MoO₃ is from about 0.9 mol % to about 30% and SiO₂ is from about 30 mol % to about 99 mol %, the glass further includes SnO₂ from about 0.01 mol % to about 5 mol %. The article may include (b) an inorganic glass-ceramic. The glass-ceramic includes at least one amorphous phase and one crystalline phase. SiO₂ is from about 1 mol % to about 95 mol %. The crystalline phase comprises an oxide, from about 0.1 mol % to about 100 mol % of the crystalline phase, of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation.

According to another feature of the present disclosure, an article includes SiO₂ from about 25 mol % to about 99 mol %, Al₂O₃ from about 0 mol % to about 50 mol %, WO₃ plus MoO₃ from about 0.35 mol % to about 30 mol %, and R₂O from about 0.1 mol % to about 50 mol %. R₂O is one or more of Li₂O, Na₂O, K₂O, Rb₂O and Cs₂O. R₂O minus Al₂O₃ is from about −35 mol % to about 7 mol %. The glass includes at least one of: (i) RO from about 0.02 mol % to about 50 mol % and (ii) SnO₂ is from about 0.01 mol % to about 5 mol %. RO is one or more of MgO, CaO, SrO, BaO and ZnO. If WO₃ is from about 1 mol % to about 30 mol %, the glass further includes Fe₂O₃ of about 0.9 mol % or less or SiO₂ is from about 60 mol % to about 99 mol %. If WO₃ is from about 0.35 mol % to about 1 mol %, the glass includes SnO₂ from about 0.01 mol % to about 5.0 mol %. If MoO₃ is from about 1 mol % to about 30 mol %, SiO₂ is from about 61 mol % to about 99 mol % or Fe₂O₃ is about 0.4 mol % or less and R₂O is greater than RO. If MoO₃ is from about 0.9 mol % to about 30% and SiO₂ is from about 30 mol % to about 99 mol %, the glass further includes SnO₂ from about 0.01 mol % to about 5 mol %.

According to another feature of the present disclosure, the article includes at least one amorphous phase and one crystalline phase. SiO₂ is from about 1 mol % to about 95 mol %. The crystalline phase comprises an oxide, from about 0.1 mol % to about 100 mol % of the crystalline phase, of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation.

According to a first aspect, an article includes (a) a glass. The glass includes SiO₂ from about 25 mol % to about 99 mol %, Al₂O₃ from about 0 mol % to about 50 mol %, WO₃ plus MoO₃ from about 0.35 mol % to about 30 mol %, and R₂O from about 0.1 mol % to about 50 mol %. R₂O is one or more of Li₂O, Na₂O, K₂O, Rb₂O and Cs₂O. R₂O minus Al₂O₃ is from about −35 mol % to about 7 mol %. The glass includes at least one of: (i) RO from about 0.02 mol % to about 50 mol % and (ii) SnO₂ is from about 0.01 mol % to about 5 mol %. RO is one or more of MgO, CaO, SrO, BaO and ZnO. If WO₃ is from about 1 mol % to about 30 mol %, the glass further includes Fe₂O₃ of about 0.9 mol % or less or SiO₂ is from about 60 mol % to about 99 mol %. If WO₃ is from about 0.35 mol % to about 1 mol %, the glass includes SnO₂ from about 0.01 mol % to about 5.0 mol %. If MoO₃ is from about 1 mol % to about 30 mol %, SiO₂ is from about 61 mol % to about 99 mol % or Fe₂O₃ is about 0.4 mol % or less and R₂O is greater than RO. If MoO₃ is from about 0.9 mol % to about 30% and SiO₂ is from about 30 mol % to about 99 mol %, the glass further includes SnO₂ from about 0.01 mol % to about 5 mol %. The article may include (b) an inorganic glass-ceramic. The glass-ceramic includes at least one amorphous phase and one crystalline phase. SiO₂ is from about 1 mol % to about 95 mol %. The crystalline phase comprises an oxide, from about 0.1 mol % to about 100 mol % of the crystalline phase, of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation.

According to a second aspect, an article includes SiO₂ from about 25 mol % to about 99 mol %, Al₂O₃ from about 0 mol % to about 50 mol %, WO₃ plus MoO₃ from about 0.35 mol % to about 30 mol %, and R₂O from about 0.1 mol % to about 50 mol %. R₂O is one or more of Li₂O, Na₂O, K₂O, Rb₂O and Cs₂O. R₂O minus Al₂O₃ is from about −35 mol % to about 7 mol %. The glass includes at least one of: (i) RO from about 0.02 mol % to about 50 mol % and (ii) SnO₂ is from about 0.01 mol % to about 5 mol %. RO is one or more of MgO, CaO, SrO, BaO and ZnO. If WO₃ is from about 1 mol % to about 30 mol %, the glass further includes Fe₂O₃ of about 0.9 mol % or less or SiO₂ is from about 60 mol % to about 99 mol %. If WO₃ is from about 0.35 mol % to about 1 mol %, the glass includes SnO₂ from about 0.01 mol % to about 5.0 mol %. If MoO₃ is from about 1 mol % to about 30 mol %, SiO₂ is from about 61 mol % to about 99 mol % or Fe₂O₃ is about 0.4 mol % or less and R₂O is greater than RO. If MoO₃ is from about 0.9 mol % to about 30% and SiO₂ is from about 30 mol % to about 99 mol %, the glass further includes SnO₂ from about 0.01 mol % to about 5 mol %.

According to a third aspect, the article of aspect 2 further comprises B₂O₃ from about 2.0 mol % to about 40 mol %, wherein SiO₂ is from about 45 mol % to about 80 mol % and Al₂O₃ is from about 0.5 mol % to about 15 mol %.

According to a fourth aspect, the article of aspect 3 is provided, wherein R₂O is from about 0 mol % to about 14 mol % and RO is from about 0 mol % to about 1 mol %.

According to a fifth aspect, the article of aspect 4 is provided, wherein MoO₃ is about 0 mol % and WO₃ is from about 1.0 mol % to about 17 mol %

According to a sixth aspect, the article of aspect 4 is provided, wherein SnO₂ is from about 0.01 mol % to about 0.4 mol %.

According to a seventh aspect, the article of aspect 4 is provided, wherein Fe₂O₃ is from about 0 mol % to about 0.2 mol %.

According to an eighth aspect, the article of aspect 2 further comprises B₂O₃ from about 5 mol % to about 20 mol %, wherein SiO₂ is from about 55 mol % to about 75 mol % and Al₂O₃ is from about 8 mol % to about 12 mol %.

According to a ninth aspect, the article of aspect 8 is provided, wherein R₂O is from about 3 mol % to about 14 mol % and RO is from about 0.5 mol % to about 4.5 mol %.

According to a tenth aspect, the article of aspect 9 is provided, wherein WO₃ is from about 1.9 mol % to about 10 mol %.

According to an eleventh aspect, the article of aspect 10 is provided, wherein MoO₃ is from about 0 mol % to about 1.0 mol %.

According to a twelfth aspect, the article of aspect 2 further comprises B₂O₃ from about 4 mol % to about 35 mol %, wherein SiO₂ is from about 55 mol % to about 75 mol % and Al₂O₃ is from about 9 mol % to about 14 mol %.

According to a thirteenth aspect, the article of aspect 12 is provided, wherein R₂O is from about 2.9 mol % to about 12.2 mol % and RO is from about 0.01 mol % to about 0.5 mol %.

According to a fourteenth aspect, the article of aspect 13 is provided, wherein MoO₃ is from about 0 mol % to about 8.2 mol % and WO₃ is from about 0 mol % to about 9 mol %.

According to a fifteenth aspect, the article of aspect 14 is provided, wherein SnO₂ is from about 0.04 mol % to about 0.4 mol %.

According to a sixteenth aspect, the article of aspect 14 is provided, wherein Fe₂O₃ is from about 0 mol % to about 0.2 mol %.

According to a seventeenth aspect, the article of aspect 14 is provided, wherein V₂O₅ is from about 0 mol % to about 0.4 mol %.

According to an eighteenth aspect, the article of aspect 2 further comprises B₂O₃ from about 5 mol % to about 25 mol %, wherein SiO₂ is from about 50 mol % to about 75 mol % and Al₂O₃ is from about 7 mol % to about 14 mol %.

According to a nineteenth aspect, the article of aspect 18 is provided, wherein R₂O is from about 5 mol % to about 14 mol % and RO is from about 0.02 mol % to about 0.5 mol %.

According to a twentieth aspect, the article of aspect 19 is provided, wherein MoO₃ is from about 1.9 mol % to about 12.1 mol % and WO₃ is from about 1.7 mol % to about 12 mol %.

According to a twenty-first aspect, the article of aspect 20 further comprises, at least one of Ag from about 0.01 mol % to about 0.75 mol %, Au from about 0.01 mol % to about 0.5 mol %, V₂O₅ from about 0.01 mol % to about 0.03 mol %, and CuO from about 0.01 mol % to about 0.75 mol %.

According to a twenty-second aspect, the article of aspect 20 is provided, wherein SnO₂ is from about 0.01 mol % to about 0.5 mol %.

According to a twenty-third aspect, the article of aspect 2 further comprises B₂O₃ from about 10 mol % to about 20 mol %, wherein SiO₂ is from about 60 mol % to about 78 mol %, and Al₂O₃ is from about 0.3 mol % to about 10 mol %.

According to a twenty-fourth aspect, the article of aspect 23 is provided, wherein R₂O is from about 0.6 mol % to about 10 mol % and RO is about 0.02 mol %.

According to a twenty-fifth aspect, the article of aspect 24 is provided, wherein MoO₃ is about 0 mol % and WO₃ is from about 1.0 mol % to about 7.0 mol %.

According to a twenty-sixth aspect, the article includes at least one amorphous phase and one crystalline phase. SiO₂ is from about 1 mol % to about 95 mol %. The crystalline phase includes an oxide, from about 0.1 mol % to about 100 mol % of the crystalline phase, of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation.

According to a twenty-seventh aspect, the article of aspect 26 is provided, wherein the crystalline phase is substantially homogenously distributed within the glass-ceramic article as a plurality of precipitates.

According to a twenty-eighth aspect, the article of aspect 26 is provided, wherein the precipitates are positioned at a depth of greater than about 10 μm from a surface of the article.

According to a twenty-ninth aspect, the article of aspect 26 is provided, wherein the crystalline phase includes a plurality of precipitates having a length of from about 1 nm to about 500 nm as measured by Electron Microscopy.

According to a thirtieth aspect, the article of aspect 26 further includes WO₃ plus MoO₃ from about 0.35 mol % to about 30 mol %, Al₂O₃ from about 0 mol % to about 50 mol %, and R₂O from about 0.1 mol % to about 50 mol %, wherein R₂O is one or more of Li₂O, Na₂O, K₂O, Rb₂O and Cs₂O, further wherein R₂O minus Al₂O₃ is from about −35 mol % to about 7 mol %.

These and other features, advantages, and objects of the present disclosure will be further understood and appreciated by those skilled in the art by reference to the following specification, claims, and appended drawings.

DETAILED DESCRIPTION

Additional features and advantages of the invention will be set forth in the detailed description which follows and will be apparent to those skilled in the art from the description, or recognized by practicing the invention as described in the following description, together with the claims and appended drawings.

As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.

In this document, relational terms, such as first and second, top and bottom, and the like, are used solely to distinguish one entity or action from another entity or action, without necessarily requiring or implying any actual such relationship or order between such entities or actions.

Modifications of the disclosure will occur to those skilled in the art and to those who make or use the disclosure. Therefore, it is understood that the embodiments shown in the drawings and described above are merely for illustrative purposes and not intended to limit the scope of the disclosure, which is defined by the following claims, as interpreted according to the principles of patent law, including the doctrine of equivalents.

It will be understood by one having ordinary skill in the art that construction of the described disclosure, and other components, is not limited to any specific material. Other exemplary embodiments of the disclosure disclosed herein may be formed from a wide variety of materials, unless described otherwise herein.

For purposes of this disclosure, the term “coupled” (in all of its forms: couple, coupling, coupled, etc.) generally means the joining of two components (electrical or mechanical) directly or indirectly to one another. Such joining may be stationary in nature or movable in nature. Such joining may be achieved with the two components (electrical or mechanical) and any additional intermediate members being integrally formed as a single unitary body with one another or with the two components. Such joining may be permanent in nature, or may be removable or releasable in nature, unless otherwise stated.

As used herein, the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. When the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. Whether or not a numerical value or end-point of a range in the specification recites “about,” the numerical value or end-point of a range is intended to include two embodiments: one modified by “about,” and one not modified by “about.” It will be further understood that the end-points of each of the ranges are significant both in relation to the other end-point, and independently of the other end-point.

Unless otherwise specified, all compositions are expressed in terms of as-batched mole percent (mol %). As will be understood by those having ordinary skill in the art, various melt constituents (e.g., fluorine, alkali metals, boron, etc.) may be subject to different levels of volatilization (e.g., as a function of vapor pressure, melt time and/or melt temperature) during melting of the constituents. As such, the term “about,” in relation to such constituents, is intended to encompass values within about 0.2 mol % when measuring final articles as compared to the as-batched compositions provided herein. With the forgoing in mind, substantial compositional equivalence between final articles and as-batched compositions is expected.

For purposes of this disclosure, the terms “bulk,” “bulk composition” and/or “overall compositions” are intended to include the overall composition of the entire article, which may be differentiated from a “local composition” or “localized composition” which may differ from the bulk composition owing to the formation of crystalline and/or ceramic phases.

As also used herein, the terms “article,” “glass-article,” “ceramic-article,” “glass-ceramics,” “glass elements,” “glass-ceramic article” and “glass-ceramic articles” may be used interchangeably, and in their broadest sense, to include any object made wholly or partly of glass and/or glass-ceramic material.

As used herein, a “glass state” refers to an inorganic amorphous phase material within the articles of the disclosure that is a product of fusion that has cooled to a rigid condition without crystallizing. As used herein, a “glass-ceramic state” refers to an inorganic material within the articles of the disclosure which includes both the glass state and a “crystalline phase” and/or “crystalline precipitates” as described herein.

Coefficients of thermal expansion (CTE) are expressed in terms of 10⁻⁷/° C. and represent a value measured over a temperature range from about 0° C. to about 300° C. unless otherwise specified.

As used herein, “transmission” and “transmittance” refer to external transmission or transmittance, which takes absorption, scattering and reflection into consideration. Fresnel reflection is not factored out of the transmission and transmittance values reported herein.

As also used herein, the term “[constituent]-free [glass or glass-ceramic]” (e.g., “cadmium and selenium-free glass-ceramic”), is indicative of a glass or a glass-ceramic that is completely free, or substantially free (i.e., <500 ppm), of the listed constituent(s) and is prepared such that the listed constituent(s) are not actively, intentionally or purposefully added or batched into the glass or glass-ceramic.

As also used herein, the terms “sharp cutoff wavelength” and “cutoff wavelength” are used interchangeably and refer to a cutoff wavelength within a range of about 350 nm to 800 nm in which the glass-ceramic has a substantially higher transmittance above the cutoff wavelength (λ_(c)) in comparison to its transmittance below the cutoff wavelength (λ_(c)). The cutoff wavelength (λ_(c)) is the wavelength at the midpoint between an “absorption limit wavelength” and a “high transmittance limit wavelength” in the given spectra for the glass-ceramic. The “absorption limit wavelength” is specified as the wavelength in which the transmittance is 5%; and in the “high transmittance wavelength” is defined as the wavelength in which the transmittance is 72%. It will be understood that a “sharp UV cutoff” as used herein may be a sharp cutoff wavelength of cutoff wavelength as described above which occurs within the ultraviolet band of the electromagnetic spectrum.

Articles of the present disclosure are composed of glass and/or glass-ceramics having one or more of the compositions outlined herein. The article can be employed in any number of applications. For example, the article can be employed in the form of substrates, elements, lenses, covers and/or other elements in any number of optics related and/or aesthetic applications.

The article is formed from an as-batched composition and is cast in a glass state. The article may later be annealed and/or thermally processed (e.g., heat treated) to form a glass-ceramic state having a plurality of ceramic or crystalline particles. It will be understood that depending on the casting technique employed, the article may readily crystalize and become a glass-ceramic without additional heat treatment (e.g., essentially be cast into the glass-ceramic state). In examples where a post-forming thermal processing is employed, a portion, a majority, substantially all or all of the article may be converted from the glass state to the glass-ceramic state. As such, although compositions of the article may be described in connection with the glass state and/or the glass-ceramic state, the bulk composition of the article may remain substantially unaltered when converted between the glass and glass-ceramic states, despite localized portions of the article have a different compositions (i.e., owing to the formation of the ceramic or crystalline precipitates).

According to various examples, the article may include Al₂O₃, SiO₂, B₂O₃, WO₃, MO₃, R₂O where R₂O is one or more of Li₂O, Na₂O, K₂O, Rb₂O and Cs₂O, RO where RO is one or more of MgO, CaO, SrO, BaO and ZnO and a number of dopants. It will be understood that a number of other constituents (e.g., F, As, Sb, Ti, P, Ce, Eu, La, Cl, Br, etc.) without departing from the teachings provided herein.

According to a first example, the article may include SiO₂ from about 58.8 mol % to about 77.58 mol %, Al₂O₃ from about 0.66 mol % to about 13.69 mol %, B₂O₃ from about 4.42 mol % to about 27 mol %, R₂O from about 0 mol % to about 13.84 mol %, RO from about 0 mol % to about 0.98 mol %, WO₃ from about 1.0 mol % to about 13.24 mol % and SnO₂ from about 0 mol % to about 0.4 mol %. Such examples of the article may be generally related to Examples 1-109 of Table 1.

According to a second example, the article may include SiO₂ from about 65.43 mol % to about 66.7 mol %, Al₂O₃ from about 9.6 mol % to about 9.98 mol %, B₂O₃ from about 9.41 mol % to about 10.56 mol %, R₂O from about 6.47 mol % to about 9.51 mol %, RO from about 0.96 mol % to about 3.85 mol %, WO₃ from about 1.92 mol % to about 3.85 mol %, MoO₃ from about 0 mol % to about 1.92 mol % and SnO₂ from about 0 mol % to about 0.1 mol %. Such examples of the article may be generally related to Examples 110-122 of Table 2.

According to a third example, the article may include SiO₂ from about 60.15 mol % to about 67.29 mol %, Al₂O₃ from about 9.0 mol % to about 13.96 mol %, B₂O₃ from about 4.69 mol % to about 20 mol %, R₂O from about 2.99 mol % to about 12.15 mol %, RO from about 0.00 mol % to about 0.14 mol %, WO₃ from about 0 mol % to about 7.03 mol %, MoO₃ from about 0 mol % to about 8.18 mol %, SnO₂ from about 0.05 mol % to about 0.15 mol % and V₂O₅ from about 0 mol % to about 0.34 mol %. Such examples of the article may be generally related to Examples 123-157 of Table 3.

According to a fourth example, the article may include SiO₂ from about 54.01 mol % to about 67.66 mol %, Al₂O₃ from about 9.55 mol % to about 11.42 mol %, B₂O₃ from about 9.36 mol % to about 15.34 mol %, R₂O from about 9.79 mol % to about 13.72 mol %, RO from about 0.00 mol % to about 0.22 mol %, WO₃ from about 1.74 mol % to about 4.48 mol %, MoO₃ from about 0 mol % to about 1.91 mol %, SnO₂ from about 0.0 mol % to about 0.21 mol %, V₂O₅ from about 0 mol % to about 0.03 mol %, Ag from about 0 mol % to about 0.48 mol % and Au from about 0 mol % to about 0.01 mol %. Such examples of the article may be generally related to Examples 158-311 of Table 4.

According to a fifth example, the article may include SiO₂ from about 60.01 mol % to about 77.94 mol %, Al₂O₃ from about 0.3 mol % to about 10.00 mol %, B₂O₃ from about 10 mol % to about 20 mol %, R₂O from about 0.66 mol % to about 10 mol %, WO₃ from about 1.0 mol % to about 6.6 mol % and SnO₂ from about 0.0 mol % to about 0.1 mol %. Such examples of the article may be generally related to Examples 312-328 of Table 5.

The article may have from about 1 mol % to about 99 mol % SiO₂, or from about 1 mol % to about 95 mol % SiO₂, or from about 45 mol % to about 80 mol % SiO₂, or from about 60 mol % to about 99 mol % SiO₂, or from about 61 mol % to about 99 mol % SiO₂, or from about 30 mol % to about 99 mol % SiO₂, or from about 58 mol % to about 78 mol % SiO₂, or from about 55 mol % to about 75 mol % SiO₂, or from about 50 mol % to about 75 mol % SiO₂, or from about 54 mol % to about 68 mol % SiO₂, or from about 60 mol % to about 78 mol % SiO₂, or from about 65 mol % to about 67 mol % SiO₂, or from about 60 mol % to about 68 mol % SiO₂, or from about 56 mol % to about 72 mol % SiO₂, or from about 60 mol % to about 70 mol % SiO2. It will be understood that any and all values and ranges between the above noted ranges of SiO₂ are contemplated. SiO₂ may serve as the primary glass-forming oxide and affect the stability, resistance to devitrification and/or viscosity of the article.

The article may include from about 0 mol % to about 50 mol % Al₂O₃, or from about 0.5 ml % to about 20 mol % Al₂O₃, or from about 0.5 mol % to about 15 mol % Al₂O₃, or from about 7 mol % to about 15 mol % Al₂O₃, or from about 0.6 mol % to about 17 mol % Al₂O₃, or from about 0.6 mol % to about 14 mol % Al₂O₃, or from about 7 mol % to about 14 mol % Al₂O₃, or from about 9.5 mol % to about 10 mol % Al₂O₃, or from about 9 mol % to about 14 mol % Al₂O₃, about 9.5 mol % to about 11.5 mol % Al₂O₃, or from about 0.3 mol % to about 10 mol % Al₂O₃, or from about 0.3 mol % to about 15 mol % Al₂O₃, or from about 2 mol % to about 16 mol % Al₂O₃, or from about 5 mol % to about 12 mol % Al₂O₃, or from about 8 mol % to about 12 mol % Al₂O₃, or from about 5 mol % to about 10 mol % Al₂O₃. It will be understood that any and all values and ranges between the above noted ranges of Al₂O₃ are contemplated. Al₂O₃ may function as a conditional network former and contributes to a stable article with low C article rigidity, and to facilitate melting and/or forming.

The article may include WO₃ and/or MoO₃. For example, WO₃ plus MoO₃ may be from about 0.35 mol % to about 30 mol %. MoO₃ may be about 0 mol % and WO₃ is from about 1.0 mol % to about 20 mol %, or MoO₃ may be about 0 mol % and WO₃ is from about 1.0 mol % to about 14 mol %, or MoO₃ is from about 0 mol % to about 8.2 mol % and WO₃ is from about 0 mol % to about 16 mol %, or MoO₃ is from about 0 mol % to about 8.2 mol % and WO₃ is from about 0 mol % to about 9 mol %, or MoO₃ is from about 1.9 mol % to about 12.1 mol % and WO₃ is from about 1.7 mol % to about 12 mol %, or MoO₃ is from about 0 mol % to about 8.2 mol % and WO₃ is from about 0 mol % to about 7.1 mol %, or MoO₃ is from about 1.9 mol % to about 12.1 mol % and WO₃ is from about 1.7 mol % to about 4.5 mol %, or MoO₃ is about 0 mol % and WO₃ is from about 1.0 mol % to about 7.0 mol %. With respect to MoO₃, the glass composition may have from about 0.35 mol % to about 30 mol % MoO₃, or from about 1 mol % to about 30 mol % MoO₃, or from about 0.9 mol % to about 30% MoO₃, or from about 0.9 mol % to about 20% MoO₃, or from about 0 mol % to about 1.0 mol % MoO₃, or from about 0 mol % to about 0.2 mol % MoO₃. With respect to WO₃, the glass composition may have from about 0.35 mol % to about 30 mol % WO₃, or from about 1 mol % to about 30 mol % WO₃, or from about 1 mol % to about 17 mol % WO₃, or from about 1.9 mol % to about 10 mol % WO₃, or from about 0.35 mol % to about 1 mol % WO₃, or from about 1.9 mol % to about 3.9 mol % WO₃, or from about 2 mol % to about 15 mol % WO₃, or from about 4 mol % to about 10 mol % of WO₃, or from about 5 mol % to about 7 mol % WO₃. It will be understood that any and all values and ranges between the above noted ranges of WO₃ and/or MoO₃ are contemplated.

The article may include from about 2 mol % to about 40 mol % of B₂O₃, or from about 4 mol % to about 40 mol % of B₂O₃, or from about 4.0 mol % to about 35 mol % B₂O₃, or from about 4.0 mol % to about 27 mol % B₂O₃, or from about 5.0 mol % to about 25 mol % B₂O₃, or from about 9.4 mol % to about 10.6 mol % B₂O₃, or from about 5 mol % to about 20 mol % B₂O₃, or from about 4.6 mol % to about 20 mol % B₂O₃, or from about 9.3 mol % to about 15.5 mol % B₂O₃, or from about 10 mol % to about 20 mol % B₂O₃, or from about 10 mol % to about 25 mol % B₂O₃. It will be understood that any and all values and ranges between the above noted ranges of B₂O₃ are contemplated. B₂O₃ may be a glass-forming oxide that is used to reduce CTE, density, and viscosity making the article easier to melt and form at low temperatures.

The article may include at least one alkali metal oxide. The alkali metal oxide may be represented by the chemical formula R₂O where R₂O is one or more of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O and/or combinations thereof. The article may have an alkali metal oxide composition of from about 0.1 mol % to about 50 mol % R₂O, or from about 0 mol % to about 14 mol % R₂O, or from about 3 mol % to about 14 mol % R₂O, or from about 5 mol % to about 14 mol % R₂O, or from about 6.4 mol % to about 9.6 mol % R₂O, or from about 2.9 mol % to about 12.2 mol % R₂O, or from about 9.7 mol % to about 12.8 mol % R₂O, or from about 0.6 mol % to about 10 mol % R₂O, or from about 0 mol % to about 15 mol % R₂O, or from about 3 mol % to about 12 mol % R₂O, or from about 7 mol % to about 10 mol % R₂O. It will be understood that any and all values and ranges between the above noted ranges of R₂O are contemplated. Alkali oxides (e.g., Li₂O, Na₂O, K₂O, Rb₂O, and Cs₂O) may be incorporated into the article for multiple reasons including: (i) reducing the melting temperature, (ii) increasing formability, (iii) enabling chemical strengthening by ion exchange and/or (iv) as a specie to partition into certain crystallites.

According to various examples, R₂O minus Al₂O₃ ranges from about from about −35 mol % to about 7 mol %, or from about −12 mol % to about 2.5 mol %, or from about −6% to about 0.25%, or from about −3.0 mol % to about 0 mol %, or from −35 mol % to about 3.8 mol %. It will be understood that any and all values and ranges between the above noted ranges of R₂O minus Al₂O₃ are contemplated. Some embodiments include an article (e.g., sheet, tape, fiber, boule), such as a glass-ceramic article, comprising at least one amorphous phase and one crystalline phase; and the glass-ceramic article further comprises SiO₂ (as a constituent) from about 1 mol % to about 95 mol %; wherein the crystalline phase comprises an oxide, from about 0.1 mol % to about 100 mol % of the crystalline phase, of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation. In some such embodiments, at least some of the crystalline phase comprises an alkali metal cation, any one or a combination of such alkali metal cations disclosed herein, in some, most, or all crystals of the crystalline phase, chemically integrated within the crystalline phase, as part of the crystalline phase.

The article may include at least one alkaline earth metal oxide. The alkaline earth metal oxide may be represented by the chemical formula RO where RO is one or more of MgO, CaO, SrO, BaO and ZnO. The article may include RO from about 0.02 mol % to about 50 mol % RO, or from about 0.01 mol % to about 5 mol % RO, or from about 0.02 mol % to about 5 mol % RO, or from about 0.05 mol % to about 10 mol % RO, or from about 0.10 mol % to about 5 mol % RO, or from about 0.15 mol % to about 5 mol % RO, or from about 0.05 mol % to about 1 mol % RO, or from about 0.5 mol % to about 4.5 mol % RO, or from about 0 mol % to about 1 mol % RO, or from about 0.96 mol % to about 3.9 mol % RO, or from about 0.2 mol % to about 2 mol % RO, or from about 0.01 mol % to about 0.5 mol % RO, or from about 0.02 mol % to about 0.22 mol % RO. It will be understood that any and all values and ranges between the above noted ranges of RO are contemplated. According to various examples, R₂O may be greater than RO. Further, the article may be free of RO. Alkaline earth oxides (e.g., MgO, CaO, SrO, and BaO) and other divalent oxides such as ZnO may improve the melting behavior of the article and can also act to increase CTE, Young's modulus, and shear modulus of the article.

The article may include from about 0.01 mol % to about 5 mol % of SnO₂, or from about 0.01 mol % to about 0.5 mol % of SnO₂, or from about 0.05 mol % to about 0.5 mol % SnO₂, or from about 0.05 mol % to about 2 mol % SnO₂, or from about 0.04 mol % to about 0.4 mol % SnO₂, or from about 0.01 mol % to about 0.4 mol % SnO₂, or from about 0.04 mol % to about 0.16 mol % SnO₂, or from about 0.01 mol % to about 0.21 mol % SnO₂, or from about 0 mol % to about 0.2 mol % SnO₂, or from about 0 mol % to about 0.1 mol % SnO₂. It will be understood that any and all values and ranges between the above noted ranges of SnO₂ are contemplated. The article may also include SnO₂ as a fining agent (e.g., other fining agents may include CeO₂, As₂O₃, Sb₂O₃, Cl—, F— or the like) in small concentrations to aid in the elimination of gaseous inclusions during melting. Certain fining agents may also act as redox couples, color centers, and or species that nucleate and or intercalate into crystallites formed in the article.

The composition of certain constituents of the article may depend on the presence and/or composition of other constituents. For example, if WO₃ is from about 1 mol % to about 30 mol %, the article further includes Fe₂O₃ of about 0.9 mol % or less or SiO₂ is from about 60 mol % to about 99 mol %. In another example, if WO₃ is from about 0.35 mol % to about 1 mol %, the article includes SnO₂ from about 0.01 mol % to about 5.0 mol %. In another example, if MoO₃ is from about 1 mol % to about 30 mol %, SiO₂ is from about 61 mol % to about 99 mol % or Fe₂O₃ is about 0.4 mol % or less and R₂O is greater than RO. In another example, if MoO₃ is from about 0.9 mol % to about 30% and SiO₂ is from about 30 mol % to about 99 mol %, the article includes SnO₂ from about 0.01 mol % to about 5 mol %.

The article may be substantially cadmium and substantially selenium free. According to various examples, the article can further include at least one dopant selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Pb, Pd, Au, Cd, Se, Ta, Bi, Ag, Ce, Pr, Nd, and Er to alter the ultraviolet, visual, color and/or near-infrared absorbance. The dopants may have concentration of from about 0.0001 mol % to about 1.0 mol % within the article. For example, the article may include at least one of Ag from about 0.01 mol % to about 0.48 mol %, Au from about 0.01 mol % to about 0.13 mol %, V₂O₅ from about 0.01 mol % to about 0.03 mol %, Fe₂O₃ from about 0 mol % to about 0.2 mol %, Fe₂O₃ from about 0 mol % to about 0.2 mol %, and CuO from about 0.01 mol % to about 0.48 mol %. According to another example, the article may include at least one of Ag from about 0.01 mol % to about 0.75 mol %, Au from about 0.01 mol % to about 0.5 mol %, V₂O₅ from about 0.01 mol % to about 0.03 mol %, and CuO from about 0.01 mol % to about 0.75 mol %. The article may include fluorine in the range of about 0 mol % to about 5 mol % to soften the glass. The article may include phosphorus from about 0 mol % to about 5 mol % to further modify physical properties of the article and modulate crystal growth. The article may include Ga₂O₃, In₂O₃ and/or GeO₂ to further modify physical and optical (e.g., refractive index) properties of the article. The following trace impurities may be present in the range of about 0.001 mol % to about 0.5 mol % to further modify the ultraviolet, visible (e.g., 390 nm to about 700 nm), and near-infrared (e.g., about 700 nm to about 2500 nm) absorbance and/or make the article fluoresce: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Se, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Te, Ta, Re, Os, Ir, Pt, Au, Ti, Pb, Bi, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Further, small additions of P₂O₅ may be made to certain compositions to further modify the physical properties and viscosity of the article.

It will be understood that each of the above noted compositions and composition ranges for SiO₂, Al₂O₃, WO₃, MoO₃, WO₃ plus MoO₃, B₂O₃, R₂O, RO, V₂O₅, Ag, Au, CuO, SnO₂, and dopants may be used with any other composition and/or composition range of the other constituents of the article as outlined herein.

As explained above, conventional formation of tungsten, molybdenum, or mixed tungsten-molybdenum containing alkali glasses has been hampered by the separation of the melt constituents during the melting process. The separation of the glass constituents during the melting process resulted in a perceived solubility limit of alkali tungstate within the molten glass, and therefore of articles cast from such melts. Conventionally, when a tungsten, molybdenum, or mixed tungsten-molybdenum melt was even slightly peralkaline (e.g., R₂O—Al₂O₃=about 0.25 mol % or greater), the melted borosilicate glass formed both a glass and a dense liquid second phase. While the concentration of the alkali tungstate second phase could be reduced by thorough mixing, melting at a high temperature, and employing a small batch size (˜1000 g), it could not be fully eliminated leading to a deleterious second crystalline phase forming. It is believed that the formation of this alkali tungstate phase occurs in the initial stages of the melt, where tungsten and/or molybdenum oxide reacts with “free” or “unbound” alkali carbonates. Due to the high density of alkali tungstate and/or alkali molybdate relative to the borosilicate glass that is formed, it rapidly segregates and/or stratifies, pooling at the bottom of the crucible and does not rapidly solubilize in the glass due to the significant difference in density. As the R₂O constituents may provide beneficial properties to the glass composition, simply decreasing the presence of the R₂O constituents within the melt may not be desirable.

It has been discovered by the inventors of the present disclosure that a homogenous single-phase W or Mo-containing peralkaline melt may be obtained through the use of “bound” alkalis. For purposes of this disclosure, “bound” alkalis are alkali elements which are bonded to alumina, boria and/or silica while “free” or “unbound” alkalis are alkali carbonates, alkali nitrates and/or alkali sulfates in which the alkali are not bound to silica, boria or alumina. Exemplary bound alkalis may include feldspar, nepheline, borax, spodumene, other sodium or potassium feldspars, alkali-alumino-silicates, alkali silicates and/or other naturally occurring and artificially created minerals containing an alkali and one or more aluminum, boron and/or silicon atoms. By introducing the alkali in the bound form, the alkalis may not react with the W or Mo present in the melt to form the dense alkali tungstate and/or alkali molybdate liquid. Moreover, this change in batch material may allow the melting of strongly peralkaline compositions (e.g., R₂O—Al₂O₃=about 2.0 mol % or more) without the formation of any alkali tungstate and/or alkali molybdate second phase. This has also allowed melt temperature and mixing method to be varied and still produce a single-phase homogenous glass. It will be understood that as the alkali tungstate phase and the borosilicate glass are not completely immiscible, prolonged stirring may also allow mixing of the two phases to cast a single phase article.

Once the glass melt is cast and solidified into the glass state article, the article may be annealed, heat treated or otherwise thermally processed to form the crystalline phase within the article. Accordingly, the article may be transformed from the glass state to the glass-ceramic state. The crystalline phase of the glass-ceramic state may take a variety of morphologies. According to various examples, the crystalline phase is formed as a plurality of precipitates within the heat treated region of the article. As such, the precipitates may have a generally crystalline structure.

As used herein, “a crystalline phase” refers to an inorganic material within the articles of the disclosure that is a solid composed of atoms, ions or molecules arranged in a pattern that is periodic in three dimensions. Further, “a crystalline phase” as referenced in this disclosure, unless expressly noted otherwise, is determined to be present using the following method. First, powder x-ray diffraction (“XRD”) is employed to detect the presence of crystalline precipitates. Second, Raman spectroscopy (“Raman”) is employed to detect the presence of crystalline precipitates in the event that XRD is unsuccessful (e.g., due to size, quantity and/or chemistry of the precipitates). Optionally, transmission electron microscopy (“TEM”) is employed to visually confirm or otherwise substantiate the determination of crystalline precipitates obtained through the XRD and/or Raman techniques. In certain circumstances, the quantity and/or size of the precipitates may be low enough that visual confirmation of the precipitates proves particularly difficult. As such, the larger sample size of XRD and Raman may be advantageous in sampling a greater quantity of material to determine the presence of the precipitates.

The crystalline precipitates may have a generally rod-like or needle-like morphology. The precipitates may have a longest length dimension of from about 1 nm to about 500 nm, or from about 1 nm to about 400 nm, or from about 1 nm to about 300 nm, or from about 1 nm to about 250 nm, or from about 1 nm to about 200 nm, or from about 1 nm to about 100 nm, or from about 1 nm to about 75 nm, or from about 1 nm to about 50 nm, or from about 1 nm to about 25 nm or from about 1 nm to about 20 nm or from about 1 nm to about 10 nm. The size of the precipitates may be measured using Electron Microscopy. For purposes of this disclosure, the term “Electron Microscopy” means visually measuring the longest length of the precipitates first by using a scanning electron microscope, and if unable to resolve the precipitates, next using a transmission electron microscope. As the crystalline precipitates may generally have a rod-like or needle-like morphology, the precipitates may have a width of from about 2 nm to about 30 nm, or from about 2 nm to about 10 nm or from about 2 nm to about 7 nm. It will be understood that the size and/or morphology of the precipitates may be uniform, substantially uniform or may vary. Generally, peraluminous compositions of the article may produce precipitates having a needle-like shape with a length of from about 100 nm to about 250 nm and a width of from about 5 nm to about 30 nm. Peralkaline compositions of the article may produce needle-like precipitates having a length of from about 10 nm to about 30 nm and a width of from about 2 nm to about 7 nm. Ag, Au and/or Cu containing examples of the article may produce rod-like precipitates having a length of from about 2 nm to about 20 nm and a width, or diameter, of from about 2 nm to about 10 nm. A volume fraction of the crystalline phase in the article may range from about 0.001% to about 20%, or from about 0.001% to about 15%, or from about 0.001% to about 10% or from about 0.001% to about 5%, or from about 0.001% to about 1%.

The relatively small size of the precipitates may be advantageous in reducing the amount of light scattered by the precipitates leading to high optical clarity of the article when in the glass-ceramic state. As will be explained in greater detail below, the size and/or quantity of the precipitates may be varied across the article such that different portions of the article may have different optical properties. For example, portions of the article where the precipitates are present may lead to changes in the absorbance, color, reflectance and/or transmission of light, as well as the refractive index as compared to portions of the article where different precipitates (e.g., size and/or quantity) and/or no precipitates are present.

The precipitates may be composed of tungsten oxide and/or molybdenum oxide. The crystalline phase includes an oxide, from about 0.1 mol % to about 100 mol % of the crystalline phase, of at least one of: (i) W, (ii) Mo, (iii) V and an alkali metal cation, and (iv) Ti and an alkali metal cation. Without being bound by theory, it is believed that during thermal processing (e.g., heat treating) of the article, tungsten and/or molybdenum cations agglomerate to form crystalline precipitates thereby transforming the glass state into the glass-ceramic state. The molybdenum and/or tungsten present in the precipitates may be reduced, or partially reduced. For example, the molybdenum and/or tungsten within the precipitates may have an oxidation state of between 0 and about +6. According to various examples, the molybdenum and/or tungsten may have a +6 oxidation state. For example, the precipitates may have the general chemical structure of WO₃ and/or MoO₃. However, there can also be a significant fraction of tungsten and or molybdenum in the +5 oxidation state and the precipitates may be known as non-stoichiometric tungsten suboxides, non-stoichiometric molybdenum suboxides, “molybdenum bronzes” and/or “tungsten bronzes.” One or more of the above-noted alkali metals and/or dopants may be present within the precipitates to compensate the +5 charge on the W or Mo. Tungsten and/or molybdenum bronzes are a group of non-stoichiometric tungsten and/or molybdenum sub-oxides that takes the general chemical form of M_(x)WO₃ or M_(x)MoO₃, where M=H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, and U, and where 0<x<1. The structures M_(x)WO₃ and M_(x)MoO₃ are considered to be a solid state defect structure in which holes in a reduced WO₃ or MoO₃ network are randomly occupied by M atoms, which are dissociated into M+ cations and free electrons. Depending on the concentration of “M,” the material properties can range from metallic to semi-conducting, thereby allowing a variety of optical absorption and electronic properties to be tuned. The more 5+W or Mo, the more M+ cations may be need to compensate and the greater the value of x.

A portion, a majority, substantially all or all of the article may be thermally processed to form the precipitates. Thermal processing techniques may include, but are not limited to, a furnace (e.g., a heat treating furnace), a microwave, a laser and/or other techniques of locally and/or bulk heating of the article. While undergoing thermal processing, the crystalline precipitates internally nucleate within the article in a homogenous manner where the article is thermally processed to transform the glass state into the glass-ceramic state. As such, in some examples, the article may include both the glass state and the glass-ceramic state. In examples where the article is thermally processed in bulk (e.g., the whole article is placed in a furnace), the precipitates may homogenously form throughout the article. In other words, the precipitates may exist from a surface of the article throughout the bulk of the article (i.e., greater than about 10 μm from the surface). In examples where the article is thermally processed locally (e.g., via a laser), the precipitates may only be present where the thermal processing reaches a sufficient temperature (e.g., at the surface and into the bulk of the article proximate the heat source). It will be understood that the article may undergo more than one thermal processing to produce the precipitates. Additionally or alternatively, thermal processing may be utilized to remove and/or alter precipitates which have already been formed (e.g., as a result of previous thermal processing). For example, thermal processing may result in the decomposition of precipitates.

According to various examples, the article may be optically transparent in the visible region of the electromagnetic spectrum (i.e., from about 400 nm to about 700 nm) both where the precipitates are present and where the precipitates are not present (i.e., in portions which are in the glass state or the glass-ceramic state). As used herein, the term “optically transparent” refers to a transmittance of greater than about 1% over a 1 mm path length (e.g., in units of %/mm) over at least one 50 nm-wide wavelength band of light in a range from about 400 nm to about 700 nm. In some examples, the article has a transmittance of about 5%/mm or greater, about 10%/mm or greater, about 15%/mm or greater, about 20%/mm or greater, about 25%/mm or greater, about 30%/mm or greater, about 40%/mm or greater, about 50%/mm or greater, about 60%/mm or greater, about 70%/mm or greater, about 80%/mm or greater and greater than all lower limits between these values, all over at least one 50 nm-wide wavelength band of light in the visible region of the spectrum.

According to various examples, the glass-ceramic state of the article absorbs light in the ultraviolet (“UV”) region (i.e., wavelengths of less than about 400 nm) based on the presence of the precipitates without the use of additional coatings or films. In some implementations, the glass-ceramic state of the article is characterized by a transmittance of less than 10%/mm, less than 9%/mm, less than 8%/mm, less than 7%/mm, less than 6%/mm, less than 5%/mm, less than 4%/mm, less than 3%/mm, less than 2%/mm, and even less than 1%/mm, for light in at least one 50 nm-wide wavelength band of light in the UV region of the spectrum (e.g., about 200 nm to about 400 nm). In some examples, the glass-ceramic state absorbs or has an absorption of at least 90%/mm, at least 91%/mm, at least 92%/mm, at least 93%/mm, at least 94%/mm, at least 95%/mm, at least 96%/mm, at least 97%/mm, at least 98%/mm, or even at least 99%/mm for light in at least one 50 nm-wide wavelength band of light in the UV region of the spectrum. The glass-ceramic state may have a sharp UV cutoff wavelength from about 320 nm to about 420 nm. For example, the glass-ceramic state may have a sharp UV cutoff at about 320 nm, about 330 nm, about 340 nm, about 350 nm, about 360 nm, about 370 nm, about 380 nm, about 390 nm, about 400 nm, about 410 nm, about 420 nm, about 430 nm or any value therebetween.

In some examples, the glass-ceramic state of the article has a transmittance of greater than about 5%/mm, greater than about 10%/mm, greater than about 15%/mm, greater than about 20%/mm, greater than about 25%/mm, greater than about 30%/mm, greater than about 40%/mm, greater than about 50%/mm, greater than about 60%/mm, greater than about 70%/mm, greater than about 80%/mm, greater than about 90%/mm and greater than all lower limits between these values, all over at least one 50 nm-wide wavelength band of light in the near-infrared region (NIR) of the spectrum (e.g., from about 700 nm to about 2700 nm). In yet other examples, the glass-ceramic state of the article has a transmittance of less than about 90%/mm, less than about 80%/mm, less than about 70%/mm, less than about 60%/mm, less than about 50%/mm, less than about 40%/mm, less than about 30%/mm, less than about 25%/mm, less than about 20%/mm, less than about 15%/mm, less than about 10%/mm, less than about 5%/mm, less than 4%/mm, less than 3%/mm, less than 2%/mm, less than 1%/mm and even less than 0.1%/mm and less than all upper limits between these values, all over at least one 50 nm-wide wavelength band of light in the NIR region of the spectrum. In other examples, the glass-ceramic state of the article absorbs or has an absorption of at least 90%/mm, at least 91%/mm, at least 92%/mm, at least 93%/mm, at least 94%/mm, at least 95%/mm, at least 96%/mm, at least 97%/mm, at least 98%/mm, or at least 99%/mm, or even at least 99.9%/mm for light in at least one 50 nm-wide wavelength band of light in the NIR region of the spectrum.

Various examples of the present disclosure may offer a variety of properties and advantages. It will be understood that although certain properties and advantages may be disclosed in connection with certain compositions, various properties and advantages disclosed may equally be applicable to other compositions.

With respect to the compositions of Tables 1 and 5 below, articles made of the disclosed compositions may exhibit a low coefficient of thermal expansion (“CTE”). For example, the article may have a coefficient of thermal expansion of from about 10×10⁻⁷° C.⁻¹ and about 60×10⁻⁷° C.⁻¹ over a temperature range of from about 0° C. to about 300° C. Such a low CTE may allow the article to withstand large and rapid fluctuations in temperature, making such articles suitable for operating in harsh environments. With respect to optical properties, the article may exhibit a less than 1% transmittance at wavelengths of about 368 nm or less, optical transparency in the visible regime (e.g., from about 500 nm to about 700 nm), and strong attenuation (e.g., blocking) of NIR wavelengths (e.g., from about 700 nm to about 1700 nm). Such articles may be advantageous over conventional NIR management solutions in that the article does not employ a coating or film (e.g., which may be mechanically fragile, sensitive to UV light and moisture). As the article is impervious to oxygen, moisture, and ultraviolet wavelengths (i.e., owing to its glass or glass-ceramic nature), the NIR absorbing precipitates may be protected from harsh environmental conditions (e.g., moisture, caustic acids, bases and gases) and rapid changes in temperature. Further, a UV cutoff wavelength and a refractive index change of the glass-ceramic state of the article may be modulatable by thermal treatment post forming. The glass-ceramic state of the article may exhibit a UV cutoff or a change in its refractive index as a result of its crystalline precipitates. The glass state of the article may have a refractive index of about between about 1.505 and about 1.508 while the glass-ceramic state of the article may have a refractive index of from about 1.520 to about 1.522. The thermally modulatable UV cutoff and refractive index may enable one tank of glass to meet multiple UV cutoff glass specifications on the fly by varying the thermal processing conditions post forming of the article. The thermally modulated refractive index can produce a large refractive index delta (10⁻²). Because the thermal treatment required to modulate the UV absorbance is done at high viscosity (e.g., between 10⁸ and 10¹² poise) finished articles can be thermally processed without marring the surface or causing deformation.

With respect to the compositions of Tables 1 and 2, articles made of these compositions may offer a novel family of non-toxic, cadmium and selenium-free articles that exhibit an optical extinction with a sharp and tunable cutoff wavelength. Unlike the Cd-free alternatives to CdSe filter glasses, which contain Se, these articles contain no Resource and Recovery Act (“RCRA”) metals or other harmful agents. Additionally, the article may be composed of lower cost elements, unlike the Cd-free alternatives that contain indium and or gallium. With respect to optical properties, articles made of these compositions may offer high transparency (e.g., greater than about 90%) over the NIR out to 2.7 microns. Further, the article may exhibit a sharp visible cutoff wavelength ranging from about 320 nm to 525 nm, which is tunable by thermal processing conditions (e.g., time and temperature), and by composition.

With respect to the compositions of Table 3, articles of these exemplary compositions may use molybdenum in lieu of tungsten which may be advantageous in that molybdenum is generally less expensive than tungsten. Additionally, articles made of these compositions may be thermally processed into the glass-ceramic state which may offer a variety of optical properties. For example, at a thickness of about 0.5 mm, the transmittance of the article of such compositions can range from about 4% to about 30% in the visible spectrum (e.g., about 400 nm to about 700 nm), about 5% to about 15% in the NIR (e.g., about 700 nm to about 1500 nm), a UV transmittance of about 1% or less at wavelengths below about 370 nm and about 5% or less at wavelengths of from about 370 nm to about 390 nm. According to some examples, mixed molybdenum-tungsten examples of the article are capable of absorbing 92.3% of the solar spectrum. Such optical properties may be visually perceived as a tint to the article. Similar to other compositions, the optical properties are generated via the growth of the precipitates and as such the tint may be varied across the article based on thermal processing. This thermally variable tint can be used to create gradients of tint within the article such as the creation of shaded edges or boarders within windshield or moonroof applications of the article. Such a feature may be advantageous in the elimination of frits which are baked onto the surface of conventional windshields and moonroofs. This thermally tunable tint can also be used to create a gradient absorption across the article. Additionally, articles created from these compositions are bleachable and patternable by lasers (e.g., operating at wavelengths of 355 nm, 810 nm, and 10.6 μm). Upon laser exposure to these wavelengths, the exposed region of the article will turn from a blue or grey color (e.g., the color being due to the precipitates) to a transparent water white or faint yellow-tint due to the thermal decomposition of the UV and NIR absorbing precipitates. By rastering the laser along the surface of the article to selectively bleach desired regions, patterns can be created within the article. When the article is bleached, the resulting glass state is no longer absorptive in the NIR such that the bleaching process is self-limiting (i.e., because the NIR absorbing precipitates have been decomposed). Furthermore, selective laser exposure may not only create patterns, but also variable UV & NIR absorbance across the article. According to yet other examples, the article may be pulverized to a sufficiently small size and functionalized to be used as a photothermal susceptor agent for cancer treatment (i.e., due to its NIR absorbing optical properties).

With respect to the compositions of Table 4, articles made of these compositions may be capable of being thermally treated after formation (e.g., to form the glass-ceramic state) to both modulate the optical absorbance and to produce a large range of colors from a single composition. Further, such examples may be capable of fusion formation and/or ion-exchanging. Conventional colored glass compositions which utilize Ag, Au and/or Cu generally rely on the formation of nanoscale metallic precipitates to generate colors. As discovered by the inventors of the present disclosure, Ag¹⁺ cations can intercalate into tungsten and molybdenum oxide forming silver tungsten bronzes and/or silver molybdenum bronzes which may provide the article with a polychromatic nature. Surprisingly, with the addition of a small concentration of Ag₂O or AgNO₃ to M_(x)WO₃ or M_(x)MoO₃ to the composition of the article many produce a variety of colors (e.g., red, orange, yellow, green, blue, various browns and/or combinations thereof) by thermally processing the article at different times and temperatures. It will be understood that Au and/or Cu may be utilized in a similar manner. Analysis demonstrates that the color tunability is not due to the formation of ensembles of metallic nanoparticles that template atop a crystalline phase (e.g., M_(x)WO₃ or M_(x)MoO₃). Rather, it is believed that the origin of color tunability in these polychromatic articles is due to the change in the band gap energy of the doped tungsten and/or molybdenum oxide precipitates, arising from the concentration of intercalated of alkali cations and Ag¹⁺, Au and/or Cu cations into the precipitates to form a pure alkali, pure metal and/or mixed alkali-metal, tungsten and/or molybdenum bronzes of varying stoichiometry. Changes in the band gap energy of the precipitates are due to its stoichiometry and in-turn is largely independent of precipitate size and/or shape. Therefore doped M_(x)WO₃ or M_(x)MoO₃ precipitates can remain the same size and/or shape, yet could be many different colors depending on the dopant “M” identity and concentration “x.” Thermally treating such articles may produce a nearly complete rainbow of colors within a single article. Further, gradients of color can be stretched or compressed over some physical distance by a thermal gradient being applied to the article. In yet other examples, the article can be laser patterned to locally alter the color of the article. Such articles may be advantageous for the production of colored sunglass lens blanks, phone and/or tablet covers and/or other products which may be composed of a glass-ceramic and may be aesthetically colored. As the precipitates are positioned within the glass-ceramic, scratch resistance and environmental durability are greater than the conventional metal and polymeric coloring layers applied to provide coloring. As the colors of the article may be altered based on thermal treatment, one tank of glass melt may be used to continuously produce blanks that can be heat treated to the specific color as customer demand dictates. Additionally, articles manufactured from these glass compositions may absorb UV and/or IR radiation similar to the other compositions disclosed herein.

According to various examples of the present disclosure, the article may be amenable to various fusion formation processes. For example, the various compositions of the present disclosure may be utilized in a single or double fusion laminate where a transparent tungsten, molybdenum, or mixed tungsten molybdenum, glass is employed as a clad material around a substrate to form the laminate article. After application as a cladding, the glass state cladding may be transformed to the glass-ceramic state. The glass-ceramic state cladding of the fusion laminate article may have a thickness of from about 50 μm to about 200 μm and may have a strong UV and IR attenuation with high average visible transmittance (e.g., from about 75% to about 85% for automotive windshields and/or architectural glazing), a strong UV and IR attenuation with low visible transmittance (e.g., about 5% to about 30% for automotive side lights, automotive sunroofs, and privacy glazing) and/or a laminate where the visible and infrared absorbance can be modulated by treatment in a gradient furnace, local heating and/or localized bleaching. Additionally, use of the compositions as a cladding to form the article provides a novel process to fully leverage the tunable optical properties while simultaneously producing a strengthened monolithic glass ply.

According to various examples, articles produced from the compositions of the present disclosure may be powdered or granulated and added to a variety of materials. For example, the powdered article may be added to a paint, binder, polymeric material (e.g., polyvinyl butyral), sol-gels and/or combinations thereof. Such a feature may be advantageous in imparting one or more of the characteristics of the article to the above mentioned material.

Examples

The following examples represent certain non-limiting examples of the composition of the articles of the disclosure.

Referring now to Table 1, the article may have SiO₂ from about 58.8 mol % to about 77.58 mol %, Al₂O₃ from about 0.66 mol % to about 13.69 mol %, B₂O₃ from about 4.42 mol % to about 27 mol %, R₂O from about 0 mol % to about 13.84 mol %, RO from about 0 mol % to about 0.98 mol %, WO₃ from about 1.0 mol % to about 13.24 mol % and SnO₂ from about 0 mol % to about 0.4 mol %. It will be understood that any of the exemplary compositions of Table 1 may include MnO₂ from about 0 mol % to about 0.2 mol %, Fe₂O₃ from about 0 mol % to about 0.1 mol %, TiO₂ from about 0 mol % to about 0.01 mol %, As₂O₅ from about 0 mol % to about 0.17 mol % and/or Eu₂O₃ from about 0 mol % to about 0.1 mol %. The compositions of Table 1 are provided in an as-batched state within a crucible.

TABLE 1 Ex. SiO₂ Al₂O₃ B₂O₃ Li₂O Na₂O K₂O Cs₂O MgO CaO ZnO SnO₂ WO₃ P₂O₅ 1 76.90 2.00 17.00 0.00 0.00 0.000 1.00 0.00 0.000 0.00 0.10 3.00 0.000 2 75.90 2.00 17.00 0.00 0.00 0.000 2.00 0.00 0.000 0.00 0.10 3.00 0.000 3 72.90 2.00 20.00 0.00 0.00 0.000 2.00 0.00 0.000 0.00 0.10 3.00 0.000 4 69.90 2.00 23.00 0.00 0.00 0.000 2.00 0.00 0.000 0.00 0.10 3.00 0.000 5 65.90 2.00 27.00 0.00 0.00 0.000 2.00 0.00 0.000 0.00 0.10 3.00 0.000 6 77.58 0.66 20.00 0.00 0.00 0.000 0.66 0.00 0.000 0.00 0.10 1.00 0.000 7 76.92 1.32 20.00 0.00 0.00 0.000 0.66 0.00 0.000 0.00 0.10 1.00 0.000 8 76.26 1.32 20.00 0.00 0.00 0.000 1.32 0.00 0.000 0.00 0.10 1.00 0.000 9 61.70 6.60 20.00 0.00 0.00 0.000 6.60 0.00 0.000 0.00 0.10 5.00 0.000 10 65.90 5.00 20.00 0.00 0.00 0.000 5.00 0.00 0.000 0.00 0.10 4.00 0.000 11 64.90 5.00 20.00 0.00 0.00 0.000 5.00 0.00 0.000 0.00 0.10 5.00 0.000 12 63.90 7.00 20.00 0.00 0.00 0.000 5.00 0.00 0.000 0.00 0.10 4.00 0.000 13 63.90 9.00 20.00 0.00 0.00 0.000 3.00 0.00 0.000 0.00 0.10 4.00 0.000 14 63.90 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 15 63.91 9.00 20.00 0.00 2.99 0.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 16 63.90 9.00 20.00 0.00 0.00 3.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 17 62.90 10.00 20.00 0.00 0.00 0.000 3.00 0.00 0.000 0.00 0.10 4.00 0.000 18 61.90 11.00 20.00 0.00 0.00 0.000 3.00 0.00 0.000 0.00 0.10 4.00 0.000 19 64.90 9.00 20.00 0.00 0.00 0.000 2.00 0.00 0.000 0.00 0.10 4.00 0.000 20 62.90 9.00 20.00 0.00 0.00 0.000 4.00 0.00 0.000 0.00 0.10 4.00 0.000 21 63.90 10.00 20.00 0.00 0.00 0.000 2.00 0.00 0.000 0.00 0.10 4.00 0.000 22 61.90 12.00 20.00 0.00 0.00 0.000 2.00 0.00 0.000 0.00 0.10 4.00 0.000 23 63.90 9.00 20.00 0.00 0.00 0.000 2.90 0.00 0.000 0.00 0.10 4.00 0.000 24 63.90 9.00 20.00 1.50 0.00 1.500 0.00 0.00 0.000 0.00 0.10 4.00 0.000 25 63.90 9.00 20.00 1.50 0.00 0.000 1.50 0.00 0.000 0.00 0.10 4.00 0.000 26 64.00 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.00 4.00 0.000 27 64.40 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 3.50 0.000 28 64.90 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 3.00 0.000 29 65.40 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 2.50 0.000 30 64.90 9.00 20.00 2.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 31 65.90 9.00 20.00 1.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 32 66.90 9.00 20.00 0.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 33 65.90 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 2.00 0.000 34 66.40 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 1.50 0.000 35 60.90 9.00 20.00 6.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 36 65.90 9.00 15.00 6.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 37 69.90 10.00 10.00 6.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 4.00 0.000 38 66.00 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.00 2.00 0.000 39 65.90 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.10 2.00 0.000 40 65.80 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.20 2.00 0.000 41 65.60 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.40 2.00 0.000 42 65.80 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.00 2.00 0.000 43 65.90 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.00 0.00 2.00 0.000 44 67.41 9.61 9.95 0.00 7.86 1.202 0.00 0.00 0.010 0.00 0.10 3.85 0.000 45 67.42 9.62 9.42 0.00 8.13 1.467 0.00 0.00 0.000 0.00 0.10 3.85 0.000 46 67.18 9.62 9.42 0.00 8.25 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 47 67.66 9.62 9.42 0.00 8.01 1.346 0.00 0.00 0.000 0.00 0.10 3.85 0.000 48 67.42 9.62 8.99 0.00 7.90 2.124 0.00 0.00 0.000 0.00 0.10 3.85 0.000 49 67.23 9.62 9.95 0.00 7.86 1.202 0.00 0.00 0.000 0.00 0.29 3.85 0.000 50 65.50 9.62 10.92 0.00 8.34 1.683 0.00 0.00 0.000 0.00 0.10 3.85 0.000 51 67.18 9.62 9.42 0.00 8.25 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 52 67.17 9.62 9.42 3.85 4.41 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 53 67.17 9.62 9.42 7.69 0.58 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 54 67.51 9.42 9.47 0.00 8.41 1.715 0.00 0.00 0.000 0.00 0.10 3.38 0.000 55 67.56 9.62 9.42 0.00 8.01 1.346 0.00 0.10 0.011 0.00 0.10 3.85 0.000 56 67.17 9.62 9.42 0.00 8.01 1.346 0.00 0.48 0.014 0.00 0.10 3.85 0.000 57 66.69 9.01 9.42 0.00 8.60 1.346 0.00 0.96 0.019 0.00 0.10 3.85 0.000 58 66.52 9.66 9.47 0.00 8.28 1.594 0.00 0.03 0.000 0.00 0.10 3.86 0.483 59 66.44 9.61 9.42 0.00 8.24 1.586 0.00 0.03 0.000 0.72 0.10 3.85 0.000 60 67.08 9.62 9.42 0.00 8.25 1.587 0.00 0.03 0.000 0.00 0.00 3.85 0.000 61 66.12 9.62 10.39 2.88 6.95 0.000 0.00 0.10 0.000 0.00 0.10 3.85 0.000 62 67.18 9.62 9.42 0.00 8.25 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 63 67.18 9.62 9.42 0.00 8.25 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 64 67.18 9.62 9.42 0.00 8.25 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 65 67.18 9.62 9.42 0.00 8.25 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 66 67.18 9.62 9.43 0.00 9.83 0.000 0.00 0.00 0.000 0.00 0.10 3.85 0.000 67 66.45 9.62 9.42 8.41 0.58 1.587 0.00 0.00 0.000 0.00 0.10 3.85 0.000 68 67.17 9.62 9.42 6.97 0.58 1.587 0.00 0.00 0.000 0.72 0.10 3.85 0.000 69 62.44 11.65 8.64 4.76 6.29 1.262 0.00 0.00 0.000 0.00 0.10 3.88 0.971 70 67.10 9.61 9.41 0.00 8.24 1.585 0.00 0.12 0.000 0.00 0.10 3.84 0.000 71 67.02 9.59 9.40 0.00 8.23 1.583 0.00 0.23 0.000 0.00 0.10 3.84 0.000 72 66.86 9.57 9.38 0.00 8.21 1.579 0.00 0.47 0.000 0.00 0.10 3.83 0.000 73 67.16 9.61 9.42 0.00 8.24 1.586 0.00 0.02 0.000 0.00 0.10 3.85 0.000 74 67.16 9.61 9.42 0.00 8.24 1.586 0.00 0.02 0.000 0.00 0.10 3.85 0.000 75 67.15 9.61 9.42 0.00 8.24 1.586 0.00 0.02 0.000 0.00 0.10 3.84 0.000 76 67.10 9.61 9.41 0.00 8.24 1.585 0.00 0.12 0.000 0.00 0.10 3.84 0.000 77 67.12 9.61 9.42 0.00 8.24 1.585 0.00 0.12 0.000 0.00 0.07 3.84 0.000 78 67.07 9.60 9.41 0.00 8.23 1.584 0.00 0.19 0.000 0.00 0.05 3.84 0.000 79 67.15 9.61 9.42 3.84 4.41 1.586 0.00 0.00 0.080 0.00 0.05 3.85 0.000 80 67.11 9.61 9.41 3.84 4.41 1.585 0.00 0.00 0.130 0.00 0.05 3.84 0.000 81 67.12 9.61 9.42 3.84 4.41 1.585 0.00 0.00 0.130 0.00 0.05 3.84 0.000 82 67.16 9.61 9.42 3.85 4.41 1.586 0.00 0.00 0.065 0.00 0.05 3.85 0.000 83 67.44 9.41 9.46 5.79 2.74 1.593 0.00 0.00 0.127 0.00 0.05 3.38 0.000 84 67.12 9.61 9.42 0.00 8.24 1.586 0.00 0.00 0.131 0.00 0.05 3.84 0.000 85 67.16 9.61 9.42 3.84 5.99 0.000 0.00 0.00 0.080 0.00 0.05 3.85 0.000 86 67.14 9.61 9.42 4.84 4.99 0.021 0.00 0.00 0.080 0.00 0.05 3.84 0.000 87 67.18 9.62 9.43 3.85 5.60 0.397 0.00 0.00 0.036 0.00 0.05 3.85 0.000 88 67.17 9.62 9.42 3.85 5.30 0.697 0.00 0.00 0.058 0.00 0.05 3.85 0.000 89 67.18 9.62 9.43 4.81 4.64 0.397 0.00 0.00 0.035 0.00 0.05 3.85 0.000 90 67.16 9.61 9.42 3.84 5.99 0.000 0.00 0.00 0.080 0.00 0.05 3.85 0.000 91 66.90 9.61 9.42 5.08 5.00 0.022 0.00 0.00 0.080 0.00 0.05 3.84 0.000 92 66.42 9.61 9.42 5.56 5.00 0.024 0.00 0.00 0.080 0.00 0.05 3.84 0.000 93 64.97 10.57 9.42 6.03 5.01 0.026 0.00 0.00 0.080 0.00 0.05 3.84 0.000 94 64.49 10.57 9.42 6.51 5.01 0.028 0.00 0.00 0.080 0.00 0.05 3.84 0.000 95 62.55 11.53 9.42 6.63 5.21 0.725 0.00 0.00 0.055 0.00 0.05 3.84 0.000 96 65.94 9.61 9.42 6.03 5.00 0.026 0.00 0.00 0.080 0.00 0.05 3.84 0.000 97 67.12 9.61 9.42 3.84 4.41 1.586 0.00 0.00 0.121 0.00 0.05 3.84 0.000 98 66.96 9.59 9.39 3.83 4.40 1.582 0.00 0.00 0.121 0.00 0.05 4.07 0.000 99 66.80 9.56 9.37 3.82 4.39 1.578 0.00 0.00 0.120 0.00 0.05 4.30 0.000 100 66.49 9.52 9.33 3.81 4.37 1.570 0.00 0.00 0.120 0.00 0.05 4.76 0.000 101 65.38 13.69 4.88 7.70 1.92 0.033 0.00 0.00 0.014 0.00 0.10 4.39 1.891 102 62.46 13.69 7.81 7.70 1.92 0.033 0.00 0.00 0.014 0.00 0.10 4.39 1.891 103 65.30 13.67 4.88 7.69 1.92 0.033 0.00 0.00 0.146 0.00 0.10 4.38 1.888 104 64.81 13.67 4.88 8.17 1.92 0.035 0.00 0.00 0.146 0.00 0.10 4.38 1.888 105 61.18 13.20 6.79 10.06 3.73 0.043 0.00 0.00 0.142 0.00 0.11 4.75 0.000 106 64.18 13.54 4.83 8.09 1.91 0.034 0.00 0.00 0.145 0.00 0.10 5.30 1.870 107 63.57 13.41 4.78 8.02 1.89 0.034 0.00 0.00 0.143 0.00 0.10 6.20 1.852 108 61.51 12.98 4.63 7.76 1.83 0.033 0.00 0.00 0.139 0.00 0.09 9.24 1.792 109 58.80 12.41 4.42 7.42 1.75 0.032 0.00 0.00 0.132 0.00 0.09 13.24 1.713

Referring now to Table 2, the article may have SiO₂ from about 65.43 mol % to about 66.7 mol %, Al₂O₃ from about 9.6 mol % to about 9.98 mol %, B₂O₃ from about 9.41 mol % to about 10.56 mol %, R₂O from about 6.47 mol % to about 9.51 mol %, RO from about 0.96 mol % to about 3.85 mol %, WO₃ from about 1.92 mol % to about 3.85 mol %, MoO₃ from about 0 mol % to about 1.92 mol % and SnO₂ from about 0 mol % to about 0.1 mol %. The compositions of Table 2 are provided in an as-batched state within a crucible.

TABLE 2 Ex. SiO₂ Al₂O₃ B₂O₃ Li₂O Na₂O K₂O Cs₂O MgO CaO SrO BaO SnO₂ WO₃ MoO₃ 110 66.70 9.62 9.42 0.00 8.01 1.346 0.00 0.96 0.000 0.000 0.000 0.10 3.85 0.00 111 66.58 9.60 9.41 0.00 7.99 1.344 0.00 0.03 0.149 0.960 0.005 0.10 3.84 0.00 112 66.67 9.61 9.42 0.00 8.00 1.346 0.00 0.03 0.011 0.008 0.961 0.10 3.85 0.00 113 66.21 9.62 9.42 0.00 8.01 1.346 0.00 1.44 0.021 0.000 0.000 0.10 3.85 0.00 114 66.69 9.98 9.42 0.00 7.65 1.346 0.00 0.96 0.017 0.000 0.000 0.10 3.85 0.00 115 66.58 9.60 9.41 0.00 0.15 9.360 0.00 0.96 0.010 0.000 0.000 0.10 3.84 0.00 116 66.65 9.61 9.42 9.37 0.06 0.000 0.00 0.96 0.000 0.000 0.000 0.10 3.84 0.00 117 66.59 9.60 9.41 0.00 0.33 0.007 9.17 0.96 0.000 0.000 0.000 0.10 3.84 0.00 118 65.43 9.60 10.56 0.00 0.15 9.361 0.00 0.96 0.000 0.000 0.000 0.10 3.84 0.00 119 66.70 9.62 9.42 0.00 7.53 0.866 0.00 1.92 0.000 0.000 0.000 0.10 3.85 0.00 120 66.70 9.62 9.42 0.00 6.47 0.000 0.00 3.85 0.000 0.000 0.000 0.10 3.85 0.00 121 66.70 9.62 9.42 0.00 8.01 1.346 0.00 0.96 0.000 0.000 0.000 0.10 2.89 0.96 122 66.70 9.62 9.42 0.00 8.01 1.346 0.00 0.96 0.000 0.000 0.000 0.10 1.92 1.92

Referring now to Table 3, the article may have SiO₂ from about 60.15 mol % to about 67.29 mol %, Al₂O₃ from about 9.0 mol % to about 13.96 mol %, B₂O₃ from about 4.69 mol % to about 20 mol %, R₂O from about 2.99 mol % to about 12.15 mol %, RO from about 0.00 mol % to about 0.14 mol %, WO₃ from about 0 mol % to about 7.03 mol %, MoO₃ from about 0 mol % to about 8.18 mol %, SnO₂ from about 0.05 mol % to about 0.15 mol % and V₂O₅ from about 0 mol % to about 0.34 mol %. It will be understood that any of the exemplary compositions of Table 3 may include Fe₂O₃ from about 0 mol % to about 0.0025 mol %. The compositions of Table 3 are provided in an as-batched state within a crucible.

TABLE 3 Ex. SiO₂ Al₂O₃ B₂O₃ Li₂O Na₂O K₂O Cs₂O MgO CaO SnO₂ WO₃ MoO₃ P₂O₅ V₂O₅ 123 63.90 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.10 0.00 4.00 0.00 0.000 124 63.91 9.00 20.00 0.00 2.99 0.000 0.00 0.00 0.000 0.10 0.00 4.00 0.00 0.000 125 63.90 9.00 20.00 0.00 0.00 3.000 0.00 0.00 0.000 0.10 0.00 4.00 0.00 0.000 126 63.90 9.00 20.00 0.00 0.00 0.000 3.00 0.00 0.000 0.10 0.00 4.00 0.00 0.000 127 64.90 9.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.10 0.00 3.00 0.00 0.000 128 62.90 11.00 20.00 3.00 0.00 0.000 0.00 0.00 0.000 0.10 0.00 3.00 0.00 0.000 129 65.31 13.96 13.47 3.07 0.00 0.000 0.00 0.00 0.000 0.10 0.00 4.09 0.00 0.000 130 60.15 13.96 13.47 4.09 0.00 0.000 0.00 0.00 0.000 0.15 0.00 8.18 0.00 0.000 131 67.17 9.62 9.42 4.84 5.00 0.021 0.00 0.02 0.019 0.05 3.61 0.24 0.00 0.000 132 67.17 9.62 9.42 4.84 5.00 0.021 0.00 0.02 0.019 0.05 3.37 0.48 0.00 0.000 133 67.17 9.62 9.42 4.84 5.00 0.021 0.00 0.02 0.019 0.05 2.88 0.96 0.00 0.000 134 67.18 9.62 9.42 4.85 5.00 0.021 0.00 0.00 0.019 0.05 1.92 1.92 0.00 0.000 135 67.18 9.62 9.42 4.85 5.00 0.021 0.00 0.00 0.019 0.05 0.96 2.89 0.00 0.000 136 65.24 11.60 7.04 4.37 7.77 0.000 0.00 0.00 0.079 0.10 2.85 0.95 0.00 0.000 137 65.24 11.60 7.04 4.37 7.77 0.000 0.00 0.00 0.079 0.10 1.90 1.90 0.00 0.000 138 67.12 9.61 9.42 3.84 4.41 1.586 0.00 0.00 0.121 0.05 2.88 0.96 0.00 0.000 139 67.12 9.61 9.42 3.84 4.41 1.586 0.00 0.00 0.121 0.05 1.92 1.92 0.00 0.000 140 66.96 9.59 9.39 3.83 4.40 1.582 0.00 0.00 0.121 0.05 2.88 1.20 0.00 0.000 141 66.80 9.56 9.37 3.82 4.39 1.578 0.00 0.00 0.121 0.05 2.87 1.43 0.00 0.000 142 66.49 9.52 9.33 3.81 4.37 1.570 0.00 0.00 0.120 0.05 2.86 1.90 0.00 0.000 143 66.96 9.59 9.39 3.83 4.40 1.582 0.00 0.00 0.121 0.05 1.92 2.16 0.00 0.000 144 66.80 9.56 9.37 3.82 4.39 1.578 0.00 0.00 0.120 0.05 1.91 2.39 0.00 0.000 145 66.64 9.54 9.35 3.82 4.38 1.574 0.00 0.00 0.120 0.05 1.91 2.62 0.00 0.000 146 67.16 9.61 9.42 4.84 5.00 0.021 0.00 0.00 0.003 0.10 2.88 0.96 0.00 0.000 147 67.15 9.61 9.42 6.77 3.08 0.029 0.00 0.00 0.002 0.10 2.88 0.96 0.00 0.000 148 62.97 13.28 4.74 7.94 1.87 0.034 0.00 0.00 0.142 0.09 6.15 0.95 1.83 0.000 149 62.38 13.16 4.69 7.87 1.85 0.034 0.00 0.00 0.140 0.09 7.03 0.94 1.82 0.000 150 67.10 9.61 9.41 3.84 4.41 1.585 0.00 0.00 0.121 0.05 2.88 0.96 0.00 0.034 151 67.10 9.61 9.41 3.84 4.41 1.585 0.00 0.00 0.121 0.05 1.92 1.92 0.00 0.034 152 67.10 9.61 9.41 3.84 4.41 1.585 0.00 0.00 0.121 0.05 3.84 0.00 0.00 0.034 153 67.11 9.61 9.41 3.84 4.41 1.585 0.00 0.00 0.121 0.05 3.84 0.00 0.00 0.029 154 67.29 9.63 9.44 4.85 4.81 0.021 0.00 0.00 0.019 0.05 3.85 0.00 0.00 0.034 155 67.15 9.61 9.42 4.84 4.99 0.021 0.00 0.00 0.019 0.05 3.85 0.00 0.00 0.038 156 67.12 9.61 9.42 4.84 4.99 0.021 0.00 0.00 0.019 0.05 3.84 0.00 0.00 0.096 157 66.96 9.58 9.39 4.83 4.98 0.021 0.00 0.00 0.019 0.05 3.83 0.00 0.00 0.335

Referring now to Table 4, the article may have SiO₂ from about 54.01 mol % to about 67.66 mol %, Al₂O₃ from about 9.55 mol % to about 11.42 mol %, B₂O₃ from about 9.36 mol % to about 15.34 mol %, R₂O from about 9.79 mol % to about 13.72 mol %, RO from about 0.00 mol % to about 0.22 mol %, WO₃ from about 1.74 mol % to about 4.48 mol %, MoO₃ from about 0 mol % to about 1.91 mol %, SnO₂ from about 0.0 mol % to about 0.21 mol %, V₂O₅ from about 0 mol % to about 0.03 mol %, Ag from about 0 mol % to about 0.48 mol % and Au from about 0 mol % to about 0.01 mol %. It will be understood that any of the exemplary compositions of Table 4 may include CeO₂ from about 0 mol % to about 0.19 mol %, CuO from about 0 mol % to about 0.48 mol %, Br— from about 0 mol % to about 0.52 mol %, Cl— from about 0 mol % to about 0.2 mol %, TiO₂ from about 0 mol % to about 0.96 mol % and/or Sb₂O₃ from about 0 mol % to about 0.29 mol %. The compositions of Table 4 are provided in an as-batched state within a crucible.

TABLE 4 Ex. SiO₂ Al₂O₃ B₂O₃ Li₂O Na₂O K₂O MgO CaO SnO₂ WO₃ MoO₃ Ag Au V₂O₅ F— 158 63.05 10.54 11.38 5.31 5.99 0.023 0.00 0.021 0.10 3.48 0.00 0.105 0.000 0.005 0.00 159 63.05 10.54 11.38 5.31 5.99 0.023 0.00 0.021 0.10 3.48 0.00 0.105 0.000 0.010 0.00 160 63.04 10.54 11.37 5.31 5.99 0.023 0.00 0.021 0.10 3.48 0.00 0.105 0.000 0.020 0.00 161 67.51 9.66 9.47 4.87 5.02 0.021 0.00 0.002 0.05 3.19 0.00 0.097 0.000 0.010 0.00 162 63.07 10.55 11.38 5.31 5.99 0.023 0.00 0.021 0.05 3.48 0.00 0.105 0.000 0.020 0.00 163 63.03 10.54 11.37 5.31 5.99 0.023 0.00 0.021 0.10 3.48 0.00 0.105 0.000 0.030 0.00 164 67.15 9.61 9.42 4.84 4.99 0.021 0.00 0.019 0.05 3.85 0.00 0.000 0.000 0.000 0.00 165 67.12 9.61 9.42 4.84 4.99 0.021 0.00 0.019 0.05 3.84 0.00 0.000 0.000 0.000 0.00 166 66.86 9.57 9.38 4.82 4.97 0.021 0.00 0.019 0.05 3.83 0.00 0.000 0.000 0.000 0.00 167 67.13 9.61 9.42 4.84 4.99 0.021 0.02 0.019 0.05 3.84 0.00 0.048 0.000 0.000 0.00 168 67.10 9.61 9.41 4.84 4.99 0.021 0.02 0.019 0.05 3.84 0.00 0.096 0.000 0.000 0.00 169 66.85 9.57 9.38 4.82 4.97 0.020 0.02 0.019 0.05 3.83 0.00 0.478 0.000 0.000 0.00 170 66.99 9.59 9.40 4.83 4.98 0.021 0.00 0.019 0.05 3.64 0.00 0.479 0.000 0.000 0.00 171 67.05 9.60 9.41 4.84 4.99 0.021 0.00 0.019 0.05 3.65 0.00 0.384 0.000 0.000 0.00 172 67.12 9.61 9.42 4.84 4.99 0.021 0.00 0.019 0.05 3.65 0.00 0.288 0.000 0.000 0.00 173 67.12 9.61 9.42 4.84 4.99 0.021 0.00 0.019 0.05 3.46 0.00 0.480 0.000 0.000 0.00 174 67.18 9.62 9.42 4.85 5.00 0.021 0.00 0.019 0.05 3.46 0.00 0.385 0.000 0.000 0.00 175 67.25 9.63 9.43 4.85 5.00 0.021 0.00 0.019 0.05 3.47 0.00 0.289 0.000 0.000 0.00 176 67.06 9.60 9.41 4.84 4.99 0.021 0.00 0.002 0.05 3.65 0.00 0.384 0.000 0.000 0.00 177 67.19 9.62 9.43 4.85 5.00 0.021 0.00 0.002 0.05 3.46 0.00 0.385 0.000 0.000 0.00 178 67.32 9.64 9.44 4.86 5.01 0.021 0.00 0.002 0.05 3.28 0.00 0.385 0.000 0.000 0.00 179 66.86 9.57 9.38 4.82 4.97 0.021 0.00 0.019 0.05 3.83 0.00 0.383 0.000 0.000 0.00 180 66.80 9.56 9.37 4.82 4.97 0.020 0.00 0.019 0.05 3.82 0.00 0.382 0.000 0.000 0.00 181 66.87 9.57 9.38 4.82 4.97 0.021 0.00 0.003 0.05 3.83 0.00 0.383 0.000 0.000 0.00 182 66.74 9.55 9.36 4.81 4.96 0.020 0.00 0.003 0.05 3.82 0.00 0.478 0.000 0.000 0.00 183 66.97 9.59 9.39 4.83 4.98 0.021 0.00 0.003 0.05 3.64 0.00 0.383 0.000 0.000 0.00 184 67.13 9.61 9.42 4.84 4.99 0.021 0.00 0.002 0.05 3.56 0.00 0.288 0.000 0.000 0.00 185 67.19 9.62 9.43 4.85 5.00 0.021 0.00 0.002 0.05 3.56 0.00 0.192 0.000 0.000 0.00 186 67.26 9.63 9.44 4.85 5.00 0.021 0.00 0.002 0.05 3.56 0.00 0.096 0.000 0.000 0.00 187 67.21 9.62 9.43 4.85 5.00 0.021 0.00 0.002 0.05 3.56 0.00 0.192 0.000 0.000 0.00 188 67.18 9.62 9.42 4.85 5.00 0.021 0.00 0.002 0.05 3.56 0.00 0.192 0.000 0.000 0.00 189 67.26 9.63 9.44 4.85 5.00 0.021 0.00 0.002 0.05 3.37 0.00 0.289 0.000 0.000 0.00 190 67.32 9.64 9.44 4.86 5.01 0.021 0.00 0.002 0.05 3.37 0.00 0.193 0.000 0.000 0.00 191 67.39 9.65 9.45 4.86 5.01 0.021 0.00 0.002 0.05 3.38 0.00 0.096 0.000 0.000 0.00 192 67.13 9.61 9.42 4.84 4.99 0.021 0.00 0.002 0.05 3.65 0.00 0.192 0.000 0.000 0.00 193 67.32 9.64 9.44 4.86 5.01 0.021 0.00 0.002 0.05 3.47 0.00 0.096 0.000 0.000 0.00 194 67.11 9.61 9.42 4.84 4.99 0.021 0.00 0.002 0.05 3.36 0.00 0.192 0.000 0.000 0.00 195 66.87 9.57 9.38 4.82 4.97 0.021 0.00 0.003 0.05 3.35 0.00 0.191 0.000 0.000 0.00 196 66.84 9.57 9.38 4.82 4.97 0.021 0.00 0.003 0.05 3.35 0.00 0.191 0.000 0.000 0.00 197 66.77 9.56 9.37 4.82 4.97 0.021 0.00 0.003 0.05 3.35 0.00 0.191 0.000 0.000 0.00 198 66.80 9.56 9.37 4.82 4.97 0.021 0.00 0.003 0.14 3.35 0.00 0.191 0.000 0.000 0.00 199 66.84 9.57 9.38 4.82 4.97 0.021 0.00 0.003 0.05 3.35 0.00 0.191 0.000 0.000 0.00 200 67.18 9.62 9.42 4.85 5.00 0.021 0.00 0.002 0.05 3.37 0.00 0.192 0.000 0.000 0.00 201 67.01 9.59 9.40 4.83 4.98 0.021 0.00 0.002 0.05 3.36 0.00 0.192 0.000 0.000 0.00 202 66.69 9.55 9.36 4.81 4.96 0.021 0.00 0.002 0.05 3.34 0.00 0.191 0.000 0.000 0.00 203 67.47 9.66 9.47 4.87 5.02 0.021 0.00 0.002 0.05 3.28 0.00 0.097 0.000 0.000 0.00 204 67.45 9.66 9.46 4.87 5.02 0.021 0.00 0.002 0.05 3.28 0.00 0.097 0.000 0.000 0.00 205 67.53 9.67 9.47 4.87 5.02 0.021 0.00 0.002 0.05 3.19 0.00 0.097 0.000 0.000 0.00 206 67.52 9.67 9.47 4.87 5.02 0.021 0.00 0.002 0.05 3.19 0.00 0.097 0.000 0.000 0.00 207 67.66 9.69 9.49 4.88 5.03 0.021 0.00 0.002 0.05 3.00 0.00 0.097 0.000 0.000 0.00 208 67.65 9.68 9.49 4.88 5.03 0.021 0.00 0.002 0.05 3.00 0.00 0.097 0.000 0.000 0.00 209 67.55 9.67 9.48 4.87 5.02 0.021 0.00 0.002 0.05 3.19 0.00 0.048 0.000 0.000 0.00 210 67.48 9.66 9.47 4.87 5.02 0.021 0.00 0.002 0.05 3.19 0.00 0.145 0.000 0.000 0.00 211 67.35 9.64 9.45 4.86 5.01 0.021 0.00 0.002 0.05 3.37 0.00 0.193 0.000 0.000 0.00 212 67.36 9.64 9.45 4.86 5.01 0.021 0.00 0.002 0.05 3.38 0.00 0.193 0.000 0.000 0.00 213 67.35 9.64 9.45 4.86 5.01 0.021 0.00 0.024 0.05 3.37 0.00 0.193 0.000 0.000 0.00 214 67.13 9.61 9.42 4.84 4.99 0.021 0.00 0.002 0.05 3.56 0.00 0.384 0.000 0.000 0.00 215 67.10 9.61 9.41 4.84 4.99 0.021 0.00 0.002 0.05 3.55 0.00 0.384 0.000 0.000 0.00 216 63.69 10.64 10.43 5.36 5.53 0.023 0.00 0.021 0.05 3.83 0.00 0.426 0.000 0.000 0.00 217 66.45 9.62 9.42 6.73 3.84 0.036 0.00 0.019 0.05 3.46 0.00 0.385 0.000 0.000 0.00 218 63.62 10.63 10.42 5.36 5.52 0.023 0.00 0.021 0.05 3.93 0.00 0.425 0.000 0.000 0.00 219 63.55 10.62 10.41 5.35 5.52 0.023 0.00 0.021 0.05 4.03 0.00 0.425 0.000 0.000 0.00 220 63.25 10.57 10.36 5.59 5.49 0.024 0.00 0.021 0.05 4.23 0.00 0.423 0.000 0.000 0.00 221 61.37 11.19 10.96 5.64 5.81 0.024 0.00 0.022 0.06 4.48 0.00 0.448 0.000 0.000 0.00 222 61.58 11.23 11.00 5.66 5.83 0.024 0.00 0.022 0.06 4.15 0.00 0.449 0.000 0.000 0.00 223 61.51 11.21 10.99 5.65 5.83 0.024 0.00 0.022 0.06 4.26 0.00 0.449 0.000 0.000 0.00 224 63.48 10.61 10.39 5.61 5.51 0.024 0.00 0.021 0.05 3.98 0.00 0.318 0.000 0.000 0.00 225 63.42 10.60 10.38 5.60 5.51 0.024 0.00 0.021 0.05 3.97 0.00 0.424 0.000 0.000 0.00 226 63.36 10.59 10.37 4.29 6.43 0.395 0.00 0.218 0.05 3.97 0.00 0.318 0.000 0.000 0.00 227 63.29 10.57 10.36 4.29 6.43 0.395 0.00 0.218 0.05 3.97 0.00 0.423 0.000 0.000 0.00 228 62.74 10.48 11.32 4.25 6.53 0.246 0.00 0.133 0.05 3.93 0.00 0.314 0.000 0.000 0.00 229 62.63 10.46 11.30 4.25 6.52 0.308 0.00 0.133 0.05 3.92 0.00 0.419 0.000 0.000 0.00 230 62.88 10.51 11.35 5.29 5.98 0.023 0.00 0.021 0.05 3.57 0.00 0.315 0.000 0.000 0.00 231 62.69 10.47 11.31 5.28 5.97 0.022 0.00 0.021 0.05 3.88 0.00 0.314 0.000 0.000 0.00 232 64.74 9.98 10.78 5.03 5.69 0.021 0.00 0.020 0.05 3.39 0.00 0.299 0.000 0.000 0.00 233 64.54 9.95 10.75 5.01 5.67 0.021 0.00 0.020 0.05 3.68 0.00 0.299 0.000 0.000 0.00 234 62.82 10.50 11.34 5.29 5.98 0.023 0.00 0.021 0.05 3.78 0.00 0.210 0.000 0.000 0.00 235 62.75 10.48 11.32 5.28 5.97 0.023 0.00 0.021 0.05 3.88 0.00 0.210 0.000 0.000 0.00 236 63.05 10.53 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.48 0.00 0.158 0.000 0.000 0.00 237 63.08 10.54 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.48 0.00 0.105 0.000 0.000 0.00 238 63.25 10.57 11.41 5.32 6.02 0.023 0.00 0.021 0.05 3.17 0.00 0.159 0.000 0.000 0.00 239 63.28 10.57 11.42 5.33 6.02 0.023 0.00 0.021 0.05 3.17 0.00 0.106 0.000 0.000 0.00 240 62.98 10.52 11.36 5.30 5.99 0.023 0.00 0.021 0.05 3.58 0.00 0.158 0.000 0.000 0.00 241 62.95 10.52 11.36 5.30 5.99 0.023 0.00 0.021 0.05 3.58 0.00 0.210 0.000 0.000 0.00 242 63.52 10.61 10.40 5.61 5.51 0.024 0.00 0.021 0.05 3.98 0.00 0.265 0.000 0.000 0.00 243 63.59 10.62 10.41 5.62 5.52 0.024 0.00 0.021 0.05 3.88 0.00 0.266 0.000 0.000 0.00 244 63.65 10.63 10.42 5.62 5.53 0.024 0.00 0.021 0.05 3.78 0.00 0.266 0.000 0.000 0.00 245 62.85 10.50 11.34 5.55 5.46 0.024 0.00 0.021 0.05 3.94 0.00 0.262 0.000 0.000 0.00 246 62.92 10.51 11.35 5.56 5.46 0.024 0.00 0.021 0.05 3.84 0.00 0.263 0.000 0.000 0.00 247 62.98 10.52 11.36 5.56 5.47 0.024 0.00 0.021 0.05 3.74 0.00 0.263 0.000 0.000 0.00 248 63.02 10.53 11.37 5.30 6.00 0.023 0.00 0.021 0.05 3.58 0.00 0.105 0.000 0.000 0.00 249 63.00 10.53 11.37 5.30 6.00 0.023 0.00 0.021 0.05 3.58 0.00 0.132 0.000 0.000 0.00 250 63.09 10.54 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.48 0.00 0.098 0.000 0.000 0.00 251 63.10 10.54 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.48 0.00 0.087 0.000 0.000 0.00 252 63.12 10.55 11.39 5.31 6.01 0.023 0.00 0.021 0.00 3.48 0.00 0.105 0.000 0.000 0.00 253 63.05 10.53 11.38 5.31 6.00 0.023 0.00 0.021 0.11 3.48 0.00 0.105 0.000 0.000 0.00 254 63.08 10.54 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.48 0.00 0.105 0.000 0.000 0.00 255 63.05 10.53 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.53 0.00 0.105 0.000 0.000 0.00 256 58.65 11.42 13.33 5.71 6.98 0.024 0.00 0.020 0.10 3.61 0.00 0.150 0.000 0.000 0.00 257 57.15 11.42 14.34 5.71 7.48 0.024 0.00 0.020 0.10 3.61 0.00 0.150 0.000 0.000 0.00 258 55.64 11.42 15.34 5.71 7.98 0.024 0.00 0.020 0.10 3.61 0.00 0.150 0.000 0.000 0.00 259 58.92 11.39 12.80 5.70 6.71 0.024 0.00 0.200 0.10 4.00 0.00 0.150 0.000 0.000 0.00 260 58.17 11.39 13.30 5.70 6.96 0.024 0.00 0.200 0.10 4.00 0.00 0.150 0.000 0.000 0.00 261 58.27 9.74 10.52 4.91 5.54 0.021 0.00 0.019 0.10 3.40 0.00 0.103 0.000 0.000 7.39 262 56.48 11.06 12.91 5.53 6.76 0.023 0.00 0.194 0.10 3.88 0.00 0.146 0.000 0.000 2.91 263 54.88 10.75 12.55 5.38 6.57 0.023 0.00 0.189 0.09 3.77 0.00 0.142 0.000 0.000 5.66 264 56.02 10.97 12.81 5.49 6.70 0.023 0.00 0.193 0.10 3.85 0.00 0.144 0.000 0.000 3.70 265 54.01 10.58 12.35 5.29 6.46 0.022 0.00 0.186 0.09 3.71 0.00 0.139 0.000 0.000 7.15 266 55.65 10.90 12.73 5.45 6.66 0.023 0.00 0.191 0.10 3.64 0.00 0.127 0.000 0.000 4.54 267 55.15 10.80 12.61 5.40 6.60 0.023 0.00 0.190 0.09 3.60 0.00 0.126 0.000 0.000 5.40 268 56.39 11.04 12.89 5.52 6.75 0.023 0.00 0.194 0.10 3.25 0.00 0.122 0.000 0.000 3.72 269 56.36 11.04 12.89 5.52 6.74 0.023 0.00 0.194 0.10 3.29 0.00 0.124 0.000 0.000 3.72 270 56.33 11.03 12.88 5.52 6.74 0.023 0.00 0.194 0.10 3.34 0.00 0.125 0.000 0.000 3.72 271 56.30 11.03 12.87 5.52 6.74 0.023 0.00 0.194 0.10 3.39 0.00 0.127 0.000 0.000 3.72 272 56.27 11.02 12.87 5.51 6.73 0.023 0.00 0.194 0.10 3.43 0.00 0.129 0.000 0.000 3.71 273 56.24 11.01 12.86 5.51 6.73 0.023 0.00 0.193 0.10 3.48 0.00 0.131 0.000 0.000 3.71 274 56.30 11.03 12.87 5.52 6.74 0.023 0.00 0.194 0.15 3.34 0.00 0.125 0.000 0.000 3.72 275 56.27 11.02 12.87 5.51 6.73 0.023 0.00 0.194 0.19 3.34 0.00 0.125 0.000 0.000 3.72 276 56.79 11.12 12.99 5.56 6.80 0.024 0.00 0.195 0.10 3.37 0.00 0.126 0.000 0.000 2.93 277 56.76 11.12 12.98 5.56 6.79 0.024 0.00 0.195 0.15 3.37 0.00 0.126 0.000 0.000 2.93 278 56.74 11.11 12.97 5.56 6.79 0.024 0.00 0.195 0.20 3.37 0.00 0.126 0.000 0.000 2.93 279 56.80 11.12 12.99 5.57 6.76 0.000 0.00 0.195 0.15 3.37 0.00 0.126 0.000 0.000 2.93 280 56.39 11.04 12.89 5.53 6.75 0.023 0.00 0.194 0.19 3.15 0.00 0.118 0.000 0.000 3.72 281 56.33 11.03 12.88 5.52 6.74 0.023 0.00 0.194 0.19 3.24 0.00 0.122 0.000 0.000 3.72 282 55.42 10.85 12.67 5.43 6.63 0.023 0.00 0.191 0.14 3.10 0.00 0.116 0.000 0.000 5.43 283 55.36 10.84 12.66 5.42 6.63 0.023 0.00 0.190 0.14 3.19 0.00 0.120 0.000 0.000 5.43 284 66.86 9.57 9.38 4.82 4.97 0.020 0.00 0.019 0.05 2.87 0.96 0.479 0.000 0.000 0.00 285 66.86 9.57 9.38 4.82 4.97 0.020 0.00 0.019 0.05 2.87 0.96 0.383 0.000 0.000 0.00 286 66.86 9.57 9.38 4.82 4.97 0.021 0.00 0.019 0.05 1.91 1.91 0.479 0.000 0.000 0.00 287 66.86 9.57 9.38 4.82 4.97 0.021 0.00 0.019 0.05 1.91 1.91 0.383 0.000 0.000 0.00 288 63.06 10.54 11.38 5.31 5.99 0.023 0.00 0.021 0.11 1.74 1.74 0.105 0.000 0.000 0.00 289 54.41 10.75 12.55 5.38 6.57 0.023 0.00 0.189 0.09 2.83 1.42 0.142 0.000 0.000 5.66 290 63.15 10.55 11.39 5.32 6.01 0.023 0.00 0.021 0.05 3.48 0.00 0.000 0.003 0.000 0.00 291 63.15 10.55 11.39 5.32 6.01 0.023 0.00 0.021 0.05 3.48 0.00 0.000 0.006 0.000 0.00 292 63.14 10.55 11.39 5.32 6.01 0.023 0.00 0.021 0.05 3.48 0.00 0.000 0.013 0.000 0.00 293 63.09 10.54 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.48 0.00 0.087 0.003 0.000 0.00 294 63.09 10.54 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.48 0.00 0.087 0.006 0.000 0.00 295 63.09 10.54 11.38 5.31 6.00 0.023 0.00 0.021 0.05 3.48 0.00 0.088 0.013 0.000 0.00 296 63.86 10.67 10.46 5.64 5.54 0.024 0.00 0.021 0.05 3.63 0.00 0.099 0.003 0.000 0.00 297 63.86 10.67 10.46 5.64 5.54 0.024 0.00 0.021 0.05 3.63 0.00 0.099 0.006 0.000 0.00 298 63.85 10.67 10.46 5.64 5.54 0.024 0.00 0.021 0.05 3.63 0.00 0.099 0.013 0.000 0.00 299 63.05 10.53 11.38 5.31 6.00 0.023 0.00 0.021 0.11 3.48 0.00 0.105 0.003 0.000 0.00 300 62.92 10.51 11.35 5.30 5.99 0.023 0.00 0.021 0.21 3.57 0.00 0.105 0.003 0.000 0.00 301 63.86 10.67 10.46 5.64 5.54 0.024 0.00 0.021 0.05 3.63 0.00 0.099 0.002 0.000 0.00 302 63.86 10.67 10.46 5.64 5.54 0.024 0.00 0.021 0.05 3.63 0.00 0.099 0.001 0.000 0.00 303 63.52 10.61 10.40 5.61 5.51 0.024 0.00 0.021 0.05 4.24 0.00 0.000 0.003 0.000 0.00 304 63.43 10.60 10.38 5.60 5.51 0.024 0.00 0.021 0.05 4.24 0.00 0.000 0.003 0.000 0.00 305 63.33 10.58 10.37 5.60 5.50 0.024 0.00 0.021 0.05 4.23 0.00 0.000 0.003 0.000 0.00 306 63.30 10.58 10.36 5.59 5.50 0.024 0.00 0.021 0.11 4.23 0.00 0.000 0.003 0.000 0.00 307 61.56 10.28 10.08 5.44 5.35 0.023 0.00 0.021 0.05 4.11 0.00 0.000 0.003 0.000 3.09 308 61.49 10.27 10.07 5.43 5.34 0.023 0.00 0.021 0.05 4.11 0.00 0.113 0.003 0.000 3.08 309 63.51 10.61 10.40 5.61 5.52 0.024 0.00 0.021 0.05 3.18 1.06 0.000 0.003 0.000 0.00 310 61.56 10.28 10.08 5.44 5.35 0.023 0.00 0.021 0.05 3.09 1.03 0.000 0.003 0.000 3.09 311 61.49 10.27 10.07 5.43 5.34 0.023 0.00 0.020 0.05 3.08 1.03 0.113 0.003 0.000 3.08

Referring now to Table 5, the article may have SiO₂ from about 60.01 mol % to about 77.94 mol %, Al₂O₃ from about 0.3 mol % to about 10.00 mol %, B₂O₃ from about 10 mol % to about 20 mol %, R₂O from about 0.66 mol % to about 10 mol %, WO₃ from about 1.0 mol % to about 6.6 mol % and SnO₂ from about 0.0 mol % to about 0.1 mol %. It will be understood that any of the exemplary compositions of Table 5 may include Sb₂O₃ from about 0 mol % to about 0.09 mol %. The compositions of Table 5 are provided in an as-batched state within a crucible.

TABLE 5 Ex. SiO₂ Al₂O3 B₂O₃ Li₂O CS₂O SnO₂ WO₃ 312 77.94 0.30 20.00 0.00 0.66 0.10 1.00 313 72.30 3.30 20.00 0.00 3.30 0.10 1.00 314 65.70 6.60 20.00 0.00 6.60 0.10 1.00 315 64.70 6.60 20.00 0.00 6.60 0.10 2.00 316 63.70 6.60 20.00 0.00 6.60 0.10 3.00 317 65.70 5.60 20.00 0.00 7.60 0.10 1.00 318 65.70 4.60 20.00 0.00 8.60 0.10 1.00 319 63.70 4.60 20.00 0.00 8.60 0.10 3.00 320 64.20 8.10 20.00 0.00 6.60 0.10 1.00 321 62.70 9.60 20.00 0.00 6.60 0.10 1.00 322 62.20 8.10 20.00 0.00 6.60 0.10 3.00 323 60.70 9.60 20.00 0.00 6.60 0.10 3.00 324 60.10 6.60 20.00 0.00 6.60 0.10 6.60 325 66.90 9.00 20.00 3.00 0.00 0.10 1.00 326 67.90 10.00 10.00 8.00 0.00 0.10 4.00 327 65.90 10.00 10.00 10.00 0.00 0.10 4.00 328 65.91 9.00 20.00 3.00 0.00 0.00 2.00

Referring now to Table 6, provided are a list of comparative exemplary glass compositions that, when melted using unbound alkali batch materials (e.g., alkali carbonates) instead of bound alkalis (e.g., nepheline), form a liquid alkali tungstate which separates during the melting process. As explained above, the second, liquid, alkali tungstate phase may solidify as a separate crystal which may opalize substrates manufactured therefrom.

TABLE 6 Ex. SiO₂ Al₂O₃ B₂O₃ Li₂O Na₂O K₂O Cs₂O CaO SnO₂ WO₃ P₂O₅ Ag 1 77.90 0.00 18.00 0.00 0.00 0.00 1.00 0.00 0.10 3.00 0.00 0.00 2 76.90 0.00 18.00 0.00 0.00 0.00 2.00 0.00 0.10 3.00 0.00 0.00 3 75.90 0.00 18.00 0.00 0.00 0.00 3.00 0.00 0.10 3.00 0.00 0.00 4 74.90 2.00 17.00 0.00 0.00 0.00 3.00 0.00 0.10 3.00 0.00 0.00 5 74.38 0.00 18.85 0.00 0.00 0.00 1.67 0.00 0.10 5.00 0.00 0.00 6 77.90 0.00 18.00 0.50 0.00 0.00 0.50 0.00 0.10 3.00 0.00 0.00 7 63.70 4.60 20.00 0.00 0.00 0.00 8.60 0.00 0.10 3.00 0.00 0.00 8 63.90 3.00 20.00 0.00 0.00 0.00 9.00 0.00 0.10 4.00 0.00 0.00 9 68.73 9.80 8.18 0.00 8.99 2.21 0.00 0.01 0.10 1.96 0.00 0.00 10 67.41 9.61 8.03 0.00 8.82 2.16 0.00 0.01 0.10 3.85 0.00 0.00 11 66.14 9.43 7.88 0.00 8.65 2.12 0.00 0.01 0.09 5.66 0.00 0.00 12 67.41 9.61 8.99 0.00 8.34 1.68 0.00 0.01 0.10 3.85 0.00 0.00 13 64.49 12.12 6.83 4.91 6.43 1.25 0.00 0.01 0.10 3.85 0.00 0.00 14 65.45 9.61 9.42 6.51 5.01 0.03 0.00 0.08 0.05 3.84 0.00 0.00 15 64.01 10.57 9.42 6.98 5.01 0.03 0.00 0.08 0.05 3.84 0.00 0.00 16 63.53 10.57 9.42 7.46 5.02 0.03 0.00 0.08 0.05 3.84 0.00 0.00 17 69.13 7.69 9.42 4.63 4.98 0.02 0.00 0.00 0.05 3.85 0.24 0.00 18 67.86 7.77 9.51 4.67 5.03 0.02 0.00 0.00 0.05 3.88 1.21 0.00 19 57.48 9.60 10.37 4.84 5.46 0.02 0.00 1.39 0.10 3.35 0.00 0.10 20 57.34 9.73 10.51 5.83 5.54 0.02 0.00 0.02 0.10 3.40 0.00 0.10 21 56.41 9.73 10.51 6.75 5.55 0.03 0.00 0.02 0.10 3.40 0.00 0.10 22 55.62 9.42 10.18 4.75 5.80 0.16 0.00 0.03 0.09 3.29 0.00 0.10 23 55.04 9.42 10.18 4.75 6.25 0.30 0.00 0.03 0.09 3.29 0.00 0.10

It will be understood that any described processes, or steps within described processes, may be combined with other disclosed processes or steps to form structures within the scope of the present disclosure. The exemplary structures and processes disclosed herein are for illustrative purposes and are not to be construed as limiting.

It is also to be understood that variations and modifications can be made on the aforementioned structures and methods without departing from the concepts of the present disclosure, and, further, it is to be understood that such concepts are intended to be covered by the following claims, unless these claims, by their language, expressly state otherwise. Further, the claims, as set forth below, are incorporated into and constitute part of this Detailed Description. 

What is claimed is:
 1. A method of making an article from glass-ceramic comprising precipitates of formula M_(x)WO₃ and/or M_(x)MoO₃, where 0<x<1 and M is a dopant cation, the method comprising: bleaching a region of the glass-ceramic such that the region has a lesser concentration of the precipitates than adjoining glass-ceramic, wherein, after the bleaching, the region is a different color than the adjoining glass-ceramic.
 2. The method of claim 1, wherein the bleaching comprises rastering a laser over the region.
 3. A glass-ceramic article comprising: precipitates of formula M_(x)WO₃ and/or M_(x)MoO₃, where 0<x<1 and M is a dopant cation; and a region of the article having a lesser concentration of the precipitates than adjoining glass-ceramic of the article, wherein the region has a different color than the adjoining glass-ceramic.
 4. The article of claim 3, wherein the precipitates have a length of from about 1 nm to about 200 nm as measured by Electron Microscopy.
 5. The article of claim 3, wherein the precipitates are homogenously distributed within the glass-ceramic adjoining the region.
 6. The article of claim 3, wherein at least some of the precipitates are at a depth of greater than about 10 μm from a surface of the article.
 7. The article of claim 3, wherein a volume fraction of precipitates in the glass-ceramic adjoining the region is from about 0.001% to about 20%.
 8. The article of claim 3, wherein the dopant cation is H, Li, Na, K, Rb, Cs, Ca, Sr, Ba, Zn, Ag, Au, Cu, Sn, Cd, In, Tl, Pb, Bi, Th, La, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, U, Ti, V, Cr, Mn, Fe, Ni, Cu, Pd, Se, Ta, Bi, and/or Ce.
 9. The article of claim 3, wherein the glass-ceramic adjoining the region has transmittance of about 1%/mm or greater over at least one 50 nm-wide wavelength band of light in a range from about 400 nm to about 700 nm.
 10. The article of claim 9, wherein the glass-ceramic adjoining the region has absorption of at least 90%/mm for light in at least one 50 nm-wide wavelength band of light in the ultraviolet portion of the spectrum.
 11. The article of claim 9, wherein the glass-ceramic adjoining the region has absorption of at least 90%/mm for light in at least one 50 nm-wide wavelength band of light in the near-infrared portion of the spectrum and the region is not absorptive in the near-infrared portion.
 12. A glass-ceramic article comprising: precipitates of formula M_(x)WO₃ and/or M_(x)MoO₃, where 0<x<1 and M is cations of Ag, Au, and/or Cu; and a region of the article having a lesser concentration of the precipitates than adjoining glass-ceramic of the article, wherein the region has a different color than the adjoining glass-ceramic.
 13. The article of claim 12, wherein the precipitates have a length of from about 1 nm to about 200 nm as measured by Electron Microscopy.
 14. The article of claim 12, wherein the precipitates are homogenously distributed within the glass-ceramic adjoining the region.
 15. The article of claim 12, wherein at least some of the precipitates are at a depth of greater than about 10 μm from a surface of the article.
 16. The article of claim 12, wherein the precipitates have a rod- or needle-morphology.
 17. The article of claim 12, wherein a volume fraction of precipitates in the glass-ceramic adjoining the region is from about 0.001% to about 20% and wherein the lesser concentration in the region is zero precipitates.
 18. The article of claim 12, wherein the glass-ceramic adjoining the region has transmittance of about 1%/mm or greater over at least one 50 nm-wide wavelength band of light in a range from about 400 nm to about 700 nm.
 19. The article of claim 18, wherein the glass-ceramic adjoining the region has absorption of at least 90%/mm for light in at least one 50 nm-wide wavelength band of light in the ultraviolet portion of the spectrum.
 20. The article of claim 18, wherein the glass-ceramic adjoining the region has absorption of at least 90%/mm for light in at least one 50 nm-wide wavelength band of light in the near-infrared portion of the spectrum and the region is not absorptive in the near-infrared portion. 